3 Carbon dioxide (B3LYP-D3/BS1, CPCM: Benzene) Note: All geometries and energies are at the B3LYP-D3/BS1(CPCM) level of theory, unless explicitly noted otherwise. G298K=-188.453647 C 0.000000000 0.000000000 0.000000000 O 0.000000000 0.000000000 1.163153000 O 0.000000000 0.000000000 -1.163153000 78 (tBuPBP)Pd(CH3) complex (B3LYP-D3/BS1, CPCM: Benzene) G298K=-1924.603142 P -2.278121000 -0.497248000 -0.055134000 P 2.282456000 -0.490906000 0.053454000 N -1.139378000 1.896226000 -0.215677000 N 1.126442000 1.904656000 0.146848000 B -0.003451000 1.029286000 -0.029282000 C -0.028981000 -3.209861000 -0.185843000 H -0.396149000 -3.519538000 -1.184859000 H -0.711375000 -3.668866000 0.554032000 H 0.950626000 -3.702154000 -0.058103000 C -2.452166000 1.354491000 -0.455356000 H -2.761224000 1.475659000 -1.507691000 H -3.229716000 1.829405000 0.167522000 C -3.384271000 -1.320429000 -1.370101000 C -4.719350000 -0.598068000 -1.630046000 H -4.579321000 0.441991000 -1.960342000 H -5.377929000 -0.592793000 -0.752458000 H -5.256280000 -1.122653000 -2.439202000 C -3.651427000 -2.784477000 -0.978931000 H -4.117463000 -3.307100000 -1.831656000 H -4.346943000 -2.863784000 -0.130515000 H -2.722239000 -3.313196000 -0.723742000 C -2.537446000 -1.296454000 -2.661643000 H -3.108620000 -1.764919000 -3.481052000 H -1.596255000 -1.849715000 -2.530362000 H -2.287645000 -0.270659000 -2.976894000 C -3.005104000 -0.624983000 1.708421000 C -2.263008000 0.416747000 2.574696000 H -2.603384000 0.315251000 3.619024000 H -2.461120000 1.452691000 2.262936000 H -1.174696000 0.257746000 2.553162000 C -4.516794000 -0.357713000 1.778179000 H -4.833897000 -0.340867000 2.835004000 H -5.099145000 -1.144293000 1.277932000 H -4.794772000 0.612866000 1.338574000 C -2.691808000 -2.022971000 2.276765000 H -1.611228000 -2.224836000 2.263167000 H -3.188558000 -2.827903000 1.719426000 H -3.043871000 -2.073766000 3.321214000 C -0.718514000 3.220142000 -0.153972000 C -1.420587000 4.418482000 -0.275937000 H -2.497855000 4.414786000 -0.460845000 C -0.710528000 5.625497000 -0.154861000 H -1.246982000 6.573745000 -0.246743000 C 0.670380000 5.630675000 0.080735000 H 1.199814000 6.582909000 0.172092000 C 1.389294000 4.428968000 0.202434000 H 2.466568000 4.433297000 0.387312000 C 0.695934000 3.225458000 0.081847000 C 2.439129000 1.374347000 0.409157000 H 2.737444000 1.526409000 1.460154000 H 3.219609000 1.837919000 -0.218253000 C 3.129242000 -0.679981000 -1.646781000 C 2.418174000 0.309987000 -2.595974000 H 2.822160000 0.179684000 -3.614036000 H 2.572488000 1.361522000 -2.312200000 H 1.334108000 0.123694000 -2.632146000 C 4.636592000 -0.382509000 -1.631479000 H 5.199387000 -1.134572000 -1.060299000 H 4.867416000 0.611423000 -1.217401000 H 5.022143000 -0.403951000 -2.665267000 C 2.879010000 -2.107204000 -2.172366000 H 3.265086000 -2.183357000 -3.203109000 H 1.806059000 -2.347160000 -2.181445000 H 3.387414000 -2.872689000 -1.571658000 C 3.287441000 -1.269900000 1.474610000 C 2.341083000 -1.215086000 2.694011000 H 2.851132000 -1.644617000 3.572970000 H 1.421056000 -1.789470000 2.507580000 H 2.050242000 -0.183594000 2.949787000 C 3.595895000 -2.742057000 1.152990000 H 4.358226000 -2.841887000 0.366527000 H 2.693231000 -3.284345000 0.838768000 H 3.992984000 -3.234478000 2.056944000 C 4.596189000 -0.532404000 1.814559000 H 5.082541000 -1.044062000 2.662953000 H 4.427481000 0.509625000 2.123682000 H 5.310773000 -0.530973000 0.981610000 Pd 0.003939000 -1.012020000 -0.051943000 81 The TS1_Out for C-CO2 bond formation with (tBuPBP)Pd(CH3) complex (B3LYP-D3/BS1, CPCM: Benzene) G298K=-2113.026411 Img. Freq.=-577.8436 cm-1 P -1.475080000 1.842812000 -0.011547000 P 1.560197000 -1.620976000 0.120393000 N -2.488819000 -0.605201000 -0.204631000 N -1.002610000 -2.314093000 0.182668000 B -1.100644000 -0.889207000 0.031556000 C 2.183738000 1.998564000 0.246445000 H 1.728648000 2.934656000 0.552484000 H 2.248991000 1.755990000 -0.814841000 H 2.703909000 1.408057000 0.995138000 C -2.949981000 0.734926000 -0.461735000 H -3.842646000 0.999070000 0.130103000 H -3.209960000 0.880328000 -1.523607000 C -1.949919000 2.549578000 1.694384000 C -1.469772000 3.144744000 -1.402994000 C -3.197494000 -1.804296000 -0.207283000 C -4.551573000 -2.072072000 -0.402058000 H -5.256813000 -1.260622000 -0.598668000 C -4.982775000 -3.407620000 -0.339565000 H -6.041357000 -3.635784000 -0.489289000 C -4.078493000 -4.448361000 -0.089235000 H -4.439847000 -5.479141000 -0.044522000 C -2.711593000 -4.189915000 0.106290000 H -2.006824000 -5.001785000 0.302726000 C -2.272511000 -2.868304000 0.043436000 C 0.256820000 -2.956040000 0.460648000 H 0.426733000 -3.848378000 -0.165369000 H 0.328472000 -3.277360000 1.513227000 C 2.873957000 -1.933802000 1.464546000 C 2.183697000 -2.031440000 -1.634826000 Pd 0.409687000 0.442874000 0.126252000 C 4.086620000 2.756480000 -0.245539000 O 4.009771000 3.950274000 -0.233948000 O 4.781213000 1.793383000 -0.430954000 C 0.940607000 -2.188385000 -2.537600000 H 0.299012000 -1.295122000 -2.505869000 H 1.277856000 -2.326731000 -3.578418000 H 0.325174000 -3.060740000 -2.272785000 C 3.018174000 -3.320890000 -1.697657000 H 3.252583000 -3.547442000 -2.751494000 H 3.974888000 -3.223125000 -1.166409000 H 2.479183000 -4.190147000 -1.289524000 C 3.006754000 -0.836675000 -2.159011000 H 3.411732000 -1.090493000 -3.153039000 H 2.374148000 0.055169000 -2.276062000 H 3.847459000 -0.555403000 -1.512546000 C 3.141076000 -3.427911000 1.734353000 H 3.543244000 -3.953270000 0.859099000 H 3.891580000 -3.511139000 2.538747000 H 2.244195000 -3.964661000 2.077146000 C 4.195769000 -1.236535000 1.097356000 H 4.869030000 -1.268621000 1.970557000 H 4.713249000 -1.746938000 0.272223000 H 4.072743000 -0.183210000 0.810683000 C 2.294345000 -1.290784000 2.743487000 H 2.145578000 -0.207889000 2.622498000 H 1.327012000 -1.733555000 3.030977000 H 2.994328000 -1.451389000 3.580405000 C -2.298512000 1.338955000 2.588265000 H -1.468630000 0.617670000 2.634793000 H -2.493008000 1.699770000 3.611923000 H -3.198064000 0.802419000 2.252571000 C -0.722244000 3.254097000 2.304449000 H -0.979767000 3.610888000 3.315758000 H 0.132181000 2.567272000 2.389500000 H -0.397104000 4.124440000 1.719183000 C -3.143422000 3.516352000 1.650420000 H -3.430490000 3.784255000 2.681352000 H -2.896807000 4.452057000 1.128974000 H -4.028743000 3.072526000 1.169070000 C -0.548398000 4.319584000 -1.031452000 H -0.435794000 4.977792000 -1.909148000 H -0.964646000 4.931886000 -0.218259000 H 0.455279000 3.981510000 -0.738992000 C -2.868497000 3.681005000 -1.763335000 H -3.336975000 4.232208000 -0.938430000 H -2.771183000 4.380890000 -2.610626000 H -3.558904000 2.886214000 -2.082247000 C -0.876484000 2.414253000 -2.628064000 H 0.153456000 2.078418000 -2.436793000 H -1.470860000 1.534415000 -2.921387000 H -0.858563000 3.104088000 -3.488226000 81 The TS1_Inn for C-CO2 bond formation with (tBuPBP)Pd complex (B3LYP-D3/BS1, CPCM: Benzene) G298K=-2113.021866 Img. Freq.=-430.0373 cm-1 P -2.292331000 0.118422000 0.205619000 P 2.284473000 -0.614892000 0.091507000 N -0.749715000 2.212995000 -0.355607000 N 1.490265000 1.794937000 -0.619113000 B 0.223969000 1.155727000 -0.369802000 C -0.421429000 -3.138658000 0.425555000 H -1.408383000 -3.442024000 0.793197000 H 0.149874000 -2.715269000 1.273459000 H 0.141250000 -4.046502000 0.154950000 C -2.157664000 1.960851000 -0.210198000 H -2.701615000 2.168519000 -1.145826000 H -2.621170000 2.580801000 0.575930000 C -3.727623000 -0.439650000 -0.921347000 C -2.774277000 0.113970000 2.056523000 C -0.107042000 3.426076000 -0.588039000 C -0.602547000 4.726177000 -0.672838000 H -1.671178000 4.924071000 -0.557866000 C 0.306995000 5.770720000 -0.907842000 H -0.062715000 6.797225000 -0.976134000 C 1.676913000 5.516404000 -1.057503000 H 2.363770000 6.346881000 -1.240891000 C 2.184311000 4.208673000 -0.981362000 H 3.251647000 4.009907000 -1.106298000 C 1.289330000 3.165827000 -0.746735000 C 2.724499000 1.055410000 -0.662640000 H 3.532120000 1.549704000 -0.096978000 H 3.087692000 0.911045000 -1.693947000 C 3.433166000 -1.823051000 -0.829253000 C 2.787617000 -0.388272000 1.932577000 Pd -0.108905000 -0.808268000 -0.067591000 C -0.982017000 -3.220602000 -1.691386000 O -0.265968000 -2.597737000 -2.422239000 O -1.891876000 -3.981546000 -1.588330000 C 2.250459000 0.976838000 2.411756000 H 1.177218000 1.092533000 2.215830000 H 2.405067000 1.052719000 3.500943000 H 2.771662000 1.826220000 1.947430000 C 4.306483000 -0.419290000 2.166497000 H 4.509628000 -0.163674000 3.220234000 H 4.735601000 -1.414167000 1.985952000 H 4.842637000 0.312645000 1.543598000 C 2.115221000 -1.492425000 2.770666000 H 2.433319000 -1.393563000 3.822077000 H 1.019734000 -1.404764000 2.743165000 H 2.381954000 -2.504316000 2.434996000 C 4.901246000 -1.365413000 -0.927644000 H 5.430149000 -1.393799000 0.031235000 H 5.432365000 -2.049328000 -1.611382000 H 5.000227000 -0.352869000 -1.347962000 C 3.347718000 -3.203503000 -0.155577000 H 3.884237000 -3.942981000 -0.773376000 H 3.814496000 -3.210976000 0.840787000 H 2.305811000 -3.540207000 -0.056905000 C 2.856433000 -1.921331000 -2.256781000 H 1.807709000 -2.240559000 -2.259116000 H 2.925035000 -0.964586000 -2.798573000 H 3.446684000 -2.658459000 -2.827048000 C -3.125316000 -0.478287000 -2.342751000 H -2.244945000 -1.128614000 -2.410792000 H -3.885700000 -0.856717000 -3.045810000 H -2.827383000 0.523717000 -2.691187000 C -4.194511000 -1.845929000 -0.508908000 H -4.883585000 -2.234878000 -1.277157000 H -3.363164000 -2.557250000 -0.427894000 H -4.746251000 -1.826937000 0.442585000 C -4.939329000 0.513970000 -0.934603000 H -5.657759000 0.147842000 -1.687572000 H -5.467769000 0.549711000 0.025082000 H -4.674140000 1.542292000 -1.221264000 C -2.687025000 -1.324276000 2.601774000 H -2.936011000 -1.314717000 3.676377000 H -3.384212000 -2.011380000 2.105247000 H -1.674949000 -1.736348000 2.492224000 C -4.172808000 0.689821000 2.329278000 H -4.968699000 0.033867000 1.951061000 H -4.317347000 0.780906000 3.419135000 H -4.311595000 1.692119000 1.895547000 C -1.720534000 0.964196000 2.795026000 H -0.709092000 0.565076000 2.641986000 H -1.722158000 2.020454000 2.487806000 H -1.933112000 0.934653000 3.876578000 81 The intermediate formed after TS1_Out with (tBuPBP)Pd complex (B3LYP-D3/BS1, CPCM: Benzene) G298K=-2113.047280 P -2.012327000 -1.311220000 0.065881000 P 2.045643000 1.014456000 -0.070838000 N -2.129260000 1.332664000 0.197058000 N -0.174198000 2.453189000 -0.248112000 B -0.725435000 1.153449000 -0.021778000 C 1.373164000 -2.944503000 -0.168286000 H 0.644314000 -3.702145000 -0.475800000 H 1.067714000 -2.484655000 0.794449000 H 1.449260000 -2.184255000 -0.975105000 C -3.012174000 0.233890000 0.485916000 H -3.943772000 0.274145000 -0.102895000 H -3.298919000 0.209705000 1.550063000 C -2.641810000 -1.811072000 -1.661384000 C -2.495592000 -2.532262000 1.445428000 C -2.418305000 2.694561000 0.113376000 C -3.619475000 3.387327000 0.255333000 H -4.547977000 2.855847000 0.478078000 C -3.601198000 4.783104000 0.105821000 H -4.532760000 5.344766000 0.212950000 C -2.409653000 5.465483000 -0.176863000 H -2.423840000 6.552704000 -0.288778000 C -1.195131000 4.776254000 -0.320152000 H -0.266920000 5.308146000 -0.542742000 C -1.203183000 3.390170000 -0.171672000 C 1.222721000 2.649490000 -0.535647000 H 1.659073000 3.487008000 0.033548000 H 1.391370000 2.855070000 -1.605152000 C 3.418606000 0.832377000 -1.376864000 C 2.691383000 1.306221000 1.696200000 Pd 0.261851000 -0.578323000 -0.032362000 C 2.812924000 -3.538612000 0.015840000 O 2.993863000 -4.662675000 -0.475178000 O 3.613430000 -2.782661000 0.620360000 C 1.543152000 1.930111000 2.518543000 H 0.637014000 1.306217000 2.497264000 H 1.871488000 2.006086000 3.568299000 H 1.271467000 2.942767000 2.185378000 C 3.906745000 2.246900000 1.738372000 H 4.171730000 2.439085000 2.791511000 H 4.789964000 1.806898000 1.256283000 H 3.700081000 3.222937000 1.271576000 C 3.041655000 -0.062218000 2.313423000 H 3.502530000 0.100581000 3.302142000 H 2.133694000 -0.666762000 2.465029000 H 3.714575000 -0.676773000 1.703148000 C 4.104999000 2.173561000 -1.708373000 H 4.597061000 2.625410000 -0.837891000 H 4.887159000 1.982805000 -2.462099000 H 3.417004000 2.914360000 -2.142038000 C 4.471817000 -0.190057000 -0.921264000 H 5.140771000 -0.405255000 -1.771664000 H 5.099660000 0.206600000 -0.109874000 H 4.042356000 -1.141766000 -0.569181000 C 2.708148000 0.306928000 -2.643068000 H 2.297728000 -0.701929000 -2.491125000 H 1.886807000 0.964042000 -2.972759000 H 3.438246000 0.249509000 -3.467096000 C -2.528134000 -0.555506000 -2.553848000 H -1.500499000 -0.162308000 -2.576654000 H -2.806519000 -0.831117000 -3.584295000 H -3.198337000 0.257725000 -2.238963000 C -1.714024000 -2.896768000 -2.240478000 H -2.055247000 -3.153063000 -3.256976000 H -0.675610000 -2.543097000 -2.315070000 H -1.714724000 -3.821315000 -1.648631000 C -4.096218000 -2.308257000 -1.658257000 H -4.422809000 -2.468546000 -2.699347000 H -4.204687000 -3.267782000 -1.133484000 H -4.790377000 -1.582594000 -1.206736000 C -2.071974000 -3.964102000 1.076126000 H -2.215665000 -4.616087000 1.953457000 H -2.680518000 -4.378845000 0.259633000 H -1.013835000 -4.025262000 0.789328000 C -4.001614000 -2.514033000 1.774209000 H -4.625000000 -2.831014000 0.929013000 H -4.187383000 -3.220046000 2.600958000 H -4.351907000 -1.527650000 2.111625000 C -1.702134000 -2.071862000 2.687808000 H -0.615810000 -2.146119000 2.531203000 H -1.932478000 -1.032850000 2.972329000 H -1.965495000 -2.715166000 3.543473000 81 The TS2 with (tBuPBP)Pd(CH3) complex (B3LYP-D3/BS1, CPCM: Benzene) G298K=-2113.048200 Img. Freq.=-24.1531 cm-1 P -2.207509000 -0.941213000 0.036283000 P 2.203955000 0.574811000 0.228456000 N -1.778177000 1.636247000 -0.417549000 N 0.302472000 2.409824000 0.188003000 B -0.468246000 1.224553000 -0.021283000 C -2.827959000 0.687835000 -0.692390000 H -2.993782000 0.562742000 -1.774732000 H -3.790241000 0.982739000 -0.241666000 C -2.843944000 -2.262285000 -1.172029000 C -4.257122000 -1.951991000 -1.704628000 H -4.289012000 -1.026893000 -2.298498000 H -5.010837000 -1.879050000 -0.909179000 H -4.564276000 -2.772058000 -2.375036000 C -2.846920000 -3.649930000 -0.507688000 H -3.003234000 -4.414927000 -1.285545000 H -3.656942000 -3.758578000 0.228026000 H -1.894456000 -3.878479000 -0.010435000 C -1.832407000 -2.255319000 -2.339733000 H -2.213969000 -2.911342000 -3.140427000 H -0.836358000 -2.629653000 -2.046389000 H -1.711985000 -1.249018000 -2.774511000 C -3.022673000 -1.016539000 1.758051000 C -2.702665000 0.315206000 2.471617000 H -3.112572000 0.273189000 3.494272000 H -3.150541000 1.187579000 1.973765000 H -1.618608000 0.487243000 2.550809000 C -4.546557000 -1.209301000 1.699084000 H -4.956421000 -1.163240000 2.722049000 H -4.826913000 -2.185464000 1.279960000 H -5.046078000 -0.422622000 1.112472000 C -2.372921000 -2.160181000 2.563751000 H -1.278947000 -2.047208000 2.619009000 H -2.591971000 -3.151847000 2.147877000 H -2.764503000 -2.140447000 3.594369000 C -1.802423000 3.030581000 -0.460141000 C -2.824154000 3.920001000 -0.788430000 H -3.810499000 3.552692000 -1.082280000 C -2.549033000 5.295586000 -0.734817000 H -3.337304000 6.008849000 -0.989037000 C -1.281977000 5.766796000 -0.363911000 H -1.094418000 6.843143000 -0.331475000 C -0.246726000 4.879116000 -0.030827000 H 0.739763000 5.246746000 0.262026000 C -0.510188000 3.511262000 -0.080437000 C 1.689139000 2.357024000 0.579663000 H 1.823579000 2.577501000 1.651678000 H 2.313378000 3.068008000 0.013812000 C 2.976047000 0.651747000 -1.509254000 C 1.979546000 1.397271000 -2.423609000 H 2.379199000 1.382421000 -3.450841000 H 1.832283000 2.450746000 -2.143060000 H 0.996983000 0.902619000 -2.444694000 C 4.325449000 1.388837000 -1.520456000 H 5.102904000 0.834592000 -0.976905000 H 4.260604000 2.406038000 -1.102515000 H 4.666947000 1.486082000 -2.564418000 C 3.139130000 -0.780899000 -2.047433000 H 3.600075000 -0.728007000 -3.048191000 H 2.174943000 -1.299125000 -2.156285000 H 3.768416000 -1.427819000 -1.424606000 C 3.444180000 0.151346000 1.604685000 C 2.589932000 -0.134028000 2.859223000 H 3.260531000 -0.336749000 3.710612000 H 1.940438000 -1.011945000 2.728247000 H 1.951680000 0.720386000 3.136903000 C 4.247360000 -1.108241000 1.230983000 H 4.982734000 -0.900185000 0.440398000 H 3.631006000 -1.954500000 0.887887000 H 4.811141000 -1.441067000 2.118700000 C 4.409372000 1.312472000 1.917211000 H 5.079743000 0.999575000 2.735323000 H 3.886837000 2.218746000 2.258802000 H 5.042570000 1.580205000 1.062312000 Pd 0.149857000 -0.645685000 0.233291000 O 1.266092000 -3.508218000 -1.867630000 C 1.888657000 -3.590652000 -0.780795000 C 1.035042000 -3.302218000 0.484897000 H 1.260083000 -2.224221000 0.684550000 H -0.026440000 -3.483597000 0.293073000 H 1.371671000 -3.822824000 1.392670000 O 3.108497000 -3.769238000 -0.581576000 81 (tBuPBP)Pd(Acatate) (B3LYP-D3/BS1, CPCM: Benzene) G298K=-2113.103313 P 2.318714000 -0.175677000 0.081081000 P -2.307319000 -0.161165000 0.014539000 N 1.165148000 2.211166000 -0.008196000 N -1.120835000 2.206485000 -0.248716000 B 0.020132000 1.343403000 -0.105137000 C 2.488204000 1.702006000 0.251905000 H 2.827007000 1.952187000 1.271472000 H 3.242676000 2.100686000 -0.447274000 C 3.255783000 -0.864715000 1.582942000 C 4.624649000 -0.205841000 1.829665000 H 4.549034000 0.880889000 1.987233000 H 5.333691000 -0.385181000 1.011611000 H 5.065373000 -0.634777000 2.745833000 C 3.417175000 -2.387543000 1.425170000 H 3.770055000 -2.810746000 2.380979000 H 4.165279000 -2.643517000 0.660689000 H 2.458611000 -2.865104000 1.169584000 C 2.330682000 -0.588809000 2.789567000 H 2.824457000 -0.942356000 3.710300000 H 1.372911000 -1.119800000 2.686097000 H 2.116432000 0.483977000 2.920362000 C 3.137499000 -0.567183000 -1.591074000 C 2.429029000 0.328863000 -2.631232000 H 2.819885000 0.083807000 -3.632710000 H 2.602365000 1.402464000 -2.464186000 H 1.342620000 0.153700000 -2.639585000 C 4.649325000 -0.293113000 -1.613336000 H 5.023697000 -0.415093000 -2.643933000 H 5.202923000 -1.002381000 -0.981593000 H 4.902086000 0.729487000 -1.291465000 C 2.858757000 -2.037706000 -1.959906000 H 1.782895000 -2.268163000 -1.958512000 H 3.358124000 -2.742282000 -1.282094000 H 3.248150000 -2.226454000 -2.974815000 C 0.733693000 3.532988000 -0.078952000 C 1.438231000 4.734128000 -0.017498000 H 2.523719000 4.736856000 0.109746000 C 0.717930000 5.935940000 -0.122879000 H 1.254593000 6.887302000 -0.077560000 C -0.673738000 5.932567000 -0.284877000 H -1.210798000 6.881344000 -0.365845000 C -1.393665000 4.727466000 -0.345140000 H -2.479262000 4.725054000 -0.471248000 C -0.688656000 3.529658000 -0.238491000 C -2.459110000 1.688058000 -0.372598000 H -2.855848000 1.820928000 -1.392477000 H -3.165746000 2.180720000 0.316806000 C -3.036017000 -0.334796000 1.765727000 C -2.256555000 0.657004000 2.657719000 H -2.601408000 0.544215000 3.699102000 H -2.415453000 1.707379000 2.370849000 H -1.174294000 0.458072000 2.635350000 C -4.539188000 -0.028656000 1.849486000 H -5.141393000 -0.781760000 1.321959000 H -4.792375000 0.963886000 1.444674000 H -4.854204000 -0.042160000 2.906867000 C -2.756648000 -1.763908000 2.274669000 H -3.040845000 -1.826109000 3.338870000 H -1.694320000 -2.033911000 2.178500000 H -3.339668000 -2.520864000 1.733670000 C -3.365214000 -0.976224000 -1.339080000 C -2.496705000 -0.892802000 -2.614091000 H -3.061291000 -1.319990000 -3.460177000 H -1.568138000 -1.469418000 -2.489653000 H -2.242152000 0.146124000 -2.879875000 C -3.604242000 -2.457391000 -0.999902000 H -4.290254000 -2.582693000 -0.149492000 H -2.659373000 -2.978205000 -0.794891000 H -4.069342000 -2.949401000 -1.870734000 C -4.714291000 -0.274515000 -1.582946000 H -5.230774000 -0.786039000 -2.412971000 H -4.599196000 0.778765000 -1.879330000 H -5.379389000 -0.315060000 -0.710716000 Pd 0.012724000 -0.639054000 0.065118000 O 0.121192000 -2.800216000 0.588937000 C -0.070267000 -3.629244000 -0.369360000 C 0.031611000 -5.101074000 0.030132000 H 1.025601000 -5.299910000 0.461877000 H -0.709815000 -5.322055000 0.814560000 H -0.135620000 -5.759021000 -0.832890000 O -0.323433000 -3.319507000 -1.545478000 74 (tBuPCP)Pd(CH3) complex (B3LYP-D3/BS1, CPCM: Benzene) G298K=-1789.687502 P 2.300571000 -0.150734000 0.087022000 C 0.003767000 1.635971000 -0.003371000 C -0.001233000 4.477350000 0.009781000 C 3.098768000 -0.174271000 -1.647745000 C -1.172601000 2.370693000 -0.293856000 C 1.178285000 2.371884000 0.292366000 C -1.174338000 3.773960000 -0.279020000 C 1.174396000 3.775419000 0.290950000 C 3.333219000 -1.113156000 1.371123000 C 0.021448000 -2.612612000 0.028179000 H -0.946029000 -3.074866000 -0.219450000 H 0.760347000 -3.023514000 -0.681029000 H 0.295148000 -2.977079000 1.035523000 C -3.096635000 -0.171527000 1.640927000 C -3.344315000 -1.112611000 -1.370414000 H -2.095794000 4.322174000 -0.502118000 H -0.003219000 5.571210000 0.015218000 H 2.094047000 4.324856000 0.518486000 C -2.430495000 1.615426000 -0.668798000 H -3.351356000 2.102553000 -0.308548000 H -2.514882000 1.571663000 -1.767425000 C 2.442345000 1.619488000 0.654529000 H 3.356191000 2.104075000 0.273414000 H 2.548145000 1.584640000 1.751593000 P -2.298536000 -0.152855000 -0.091378000 Pd 0.001065000 -0.468460000 -0.000433000 C -2.417173000 -1.293193000 -2.591954000 H -1.528250000 -1.887587000 -2.336856000 H -2.967670000 -1.810658000 -3.396070000 H -2.071155000 -0.328129000 -2.995475000 C -4.613661000 -0.356728000 -1.811096000 H -4.385348000 0.608716000 -2.285040000 H -5.148899000 -0.965557000 -2.560093000 H -5.308833000 -0.173890000 -0.981296000 C -3.744664000 -2.501442000 -0.841650000 H -4.489565000 -2.440893000 -0.035716000 H -4.199758000 -3.081073000 -1.662888000 H -2.879066000 -3.068673000 -0.473488000 C -2.768887000 -1.515502000 2.321214000 H -3.138274000 -1.495260000 3.360777000 H -3.240558000 -2.371122000 1.820164000 H -1.683535000 -1.694351000 2.342726000 C -2.426624000 0.956115000 2.455195000 H -1.332154000 0.849645000 2.474028000 H -2.657817000 1.956018000 2.059879000 H -2.797423000 0.912098000 3.493231000 C -4.615681000 0.063067000 1.625828000 H -5.163416000 -0.760582000 1.147000000 H -4.981511000 0.136768000 2.664416000 H -4.886079000 1.001936000 1.117779000 C 2.462112000 0.980304000 -2.450901000 H 1.364383000 0.914310000 -2.458550000 H 2.734970000 1.969881000 -2.056276000 H 2.819987000 0.925977000 -3.493012000 C 4.624112000 0.013578000 -1.631392000 H 5.145492000 -0.841744000 -1.179003000 H 4.926168000 0.927905000 -1.097333000 C 2.735915000 -1.499205000 -2.346338000 H 1.645713000 -1.621597000 -2.420933000 H 3.154401000 -1.496257000 -3.367341000 H 3.138042000 -2.378592000 -1.825588000 C 2.443876000 -1.193214000 2.631508000 H 1.501659000 -1.720159000 2.428738000 H 2.985023000 -1.737356000 3.424115000 H 2.194420000 -0.196441000 3.028492000 C 4.658779000 -0.423076000 1.746828000 H 5.154506000 -1.011014000 2.538583000 H 5.358326000 -0.357097000 0.904442000 H 4.506101000 0.590638000 2.145538000 C 3.616708000 -2.541331000 0.872783000 H 4.326111000 -2.553638000 0.032564000 H 4.071661000 -3.126018000 1.690593000 H 2.697179000 -3.056262000 0.562514000 H 4.988550000 0.105032000 -2.669056000 77 The TS1_Out for C-CO2 bond formation with (tBuPCP)Pd(CH3) complex (B3LYP-D3/BS1, CPCM: Benzene) G298K=-1978.103064 Img. Freq.=-623.5928 cm-1 P -2.284238000 -0.329973000 0.130040000 C 0.099906000 -1.994044000 -0.149497000 C 0.219612000 -4.801771000 -0.486791000 C -3.020562000 -0.111932000 -1.614124000 C 1.306854000 -2.628439000 -0.533561000 C -1.048424000 -2.798934000 0.050948000 C 1.360805000 -4.021789000 -0.689140000 C -0.982520000 -4.189511000 -0.124488000 C -3.377310000 0.450885000 1.483909000 C -0.053567000 2.374072000 0.459709000 H 0.952123000 2.546281000 0.822657000 H -0.245257000 2.221405000 -0.604756000 H -0.866679000 2.364996000 1.176269000 C 3.184641000 -0.248478000 1.657162000 C 3.262726000 1.064736000 -1.236875000 H 2.301973000 -4.498957000 -0.980265000 H 0.266433000 -5.886795000 -0.614777000 H -1.878994000 -4.798416000 0.029834000 C 2.529616000 -1.787746000 -0.829703000 H 3.471020000 -2.279925000 -0.537473000 H 2.595628000 -1.615267000 -1.916485000 C -2.345651000 -2.153840000 0.488483000 H -3.232983000 -2.634190000 0.045633000 H -2.454383000 -2.249763000 1.581427000 C -0.418487000 4.258182000 -0.163775000 O 0.641400000 4.766708000 -0.415042000 O -1.612920000 4.409472000 -0.163996000 P 2.341966000 -0.110756000 -0.045307000 Pd 0.021437000 0.054978000 0.124677000 C 2.304971000 1.282891000 -2.428766000 H 1.397307000 1.821918000 -2.124002000 H 2.814430000 1.890359000 -3.195097000 H 1.998730000 0.337823000 -2.904573000 C 4.580710000 0.456340000 -1.758433000 H 4.427280000 -0.493280000 -2.291308000 H 5.033881000 1.159923000 -2.477084000 H 5.315248000 0.287372000 -0.960931000 C 3.553996000 2.430195000 -0.587931000 H 4.256735000 2.352906000 0.253703000 H 4.024221000 3.083111000 -1.342463000 H 2.642695000 2.944183000 -0.251758000 C 2.784467000 0.970126000 2.512400000 H 3.238704000 0.873333000 3.512816000 H 3.126659000 1.922353000 2.084848000 H 1.693012000 1.026899000 2.637836000 C 2.622961000 -1.517663000 2.333375000 H 1.524001000 -1.505471000 2.378838000 H 2.927872000 -2.440584000 1.818747000 H 3.009222000 -1.568420000 3.365066000 C 4.715429000 -0.360436000 1.574369000 H 5.182964000 0.561749000 1.201935000 H 5.118297000 -0.545224000 2.584666000 H 5.037946000 -1.197769000 0.936143000 C -2.354408000 -1.158866000 -2.532031000 H -1.257245000 -1.091340000 -2.503425000 H -2.635728000 -2.189557000 -2.270294000 H -2.683073000 -0.976559000 -3.568892000 C -4.544200000 -0.313162000 -1.661039000 H -5.088660000 0.471954000 -1.119077000 H -4.846558000 -1.291987000 -1.257166000 C -2.647430000 1.292293000 -2.133293000 H -1.559492000 1.384600000 -2.269648000 H -3.118683000 1.449516000 -3.117979000 H -2.968204000 2.108305000 -1.472724000 C -2.514872000 0.450604000 2.765390000 H -1.611470000 1.065954000 2.655628000 H -3.108120000 0.858976000 3.600437000 H -2.195544000 -0.563683000 3.053249000 C -4.658764000 -0.362743000 1.757395000 H -5.216042000 0.122678000 2.576566000 H -5.328699000 -0.406905000 0.889882000 H -4.444308000 -1.392313000 2.079533000 C -3.758828000 1.899527000 1.126270000 H -4.479378000 1.941085000 0.296940000 H -4.247063000 2.363014000 2.000167000 H -2.900946000 2.531009000 0.855297000 H -4.878763000 -0.275789000 -2.711566000 77 The TS1_Inn for C-CO2 bond formation with (tBuPCP)Pd(CH3) complex (B3LYP-D3/BS1, CPCM: Benzene) G298K=-1978.087519 Img. Freq.=-489.6377 cm-1 P -2.284679000 0.226423000 0.102301000 P 2.370821000 -0.066316000 0.008660000 C -0.080624000 -2.498655000 0.947805000 H -1.002885000 -2.781285000 1.463454000 H 0.447361000 -1.756195000 1.577992000 H 0.607557000 -3.356734000 0.932605000 C -2.391282000 1.812576000 -0.853707000 H -2.895046000 1.582539000 -1.805798000 H -3.032836000 2.548302000 -0.343854000 C -3.709696000 -0.808366000 -0.639694000 C -2.637104000 0.732757000 1.914667000 C 2.633369000 1.220843000 -1.291418000 H 3.534970000 1.825352000 -1.104802000 H 2.805346000 0.674001000 -2.233338000 C 3.621474000 -1.440488000 -0.430407000 C 2.837895000 0.796019000 1.661089000 Pd 0.002779000 -0.341816000 -0.126778000 C -0.639005000 -3.165597000 -0.935260000 O -0.051839000 -2.665000000 -1.860462000 O -1.435007000 -4.008513000 -0.636709000 C 2.229488000 2.213189000 1.662384000 H 1.155768000 2.208221000 1.440895000 H 2.371176000 2.654921000 2.662992000 H 2.715552000 2.877996000 0.934260000 C 4.354156000 0.936418000 1.875220000 H 4.528719000 1.528417000 2.789618000 H 4.854039000 -0.030957000 2.015699000 H 4.842877000 1.468148000 1.044865000 C 2.219393000 -0.000799000 2.826355000 H 2.511770000 0.465726000 3.782075000 H 1.121223000 0.006709000 2.775115000 H 2.551557000 -1.047983000 2.852508000 C 5.023305000 -0.907214000 -0.787656000 H 5.551563000 -0.459985000 0.061400000 H 5.635322000 -1.754173000 -1.141987000 H 4.993167000 -0.170598000 -1.604497000 C 3.717804000 -2.451335000 0.726187000 H 4.332002000 -3.309204000 0.404985000 H 4.196826000 -2.025331000 1.619321000 H 2.730161000 -2.838984000 1.012855000 C 3.050987000 -2.154384000 -1.671163000 H 2.049196000 -2.561194000 -1.498463000 H 2.986388000 -1.483954000 -2.542815000 H 3.727157000 -2.980994000 -1.947324000 C -3.234972000 -1.218155000 -2.050955000 H -2.265336000 -1.727218000 -2.046077000 H -3.977087000 -1.903134000 -2.493061000 H -3.151611000 -0.350089000 -2.723908000 C -3.963628000 -2.061027000 0.215815000 H -4.697026000 -2.703098000 -0.300429000 H -3.056457000 -2.659983000 0.360745000 H -4.391303000 -1.805264000 1.196371000 C -5.029231000 -0.023335000 -0.794018000 H -5.737096000 -0.650876000 -1.361646000 H -5.504437000 0.211415000 0.165048000 H -4.908273000 0.913097000 -1.358245000 C -2.286297000 -0.434287000 2.856693000 H -2.486870000 -0.128553000 3.897429000 H -2.877804000 -1.337271000 2.655603000 H -1.224910000 -0.705684000 2.785181000 C -4.090327000 1.171655000 2.155850000 H -4.793473000 0.330452000 2.089482000 H -4.173404000 1.585232000 3.175219000 H -4.416853000 1.956429000 1.456533000 C -1.699516000 1.912559000 2.240955000 H -0.647699000 1.649223000 2.070526000 H -1.923296000 2.813225000 1.650813000 H -1.813734000 2.175393000 3.305785000 C -1.013813000 2.350065000 -1.152204000 C -0.896794000 3.655784000 -1.656394000 C 0.131481000 1.531209000 -0.989561000 C 0.344135000 4.167096000 -2.033432000 H -1.795266000 4.272311000 -1.759597000 C 1.382819000 2.060156000 -1.404265000 C 1.478323000 3.362361000 -1.915062000 H 0.427700000 5.185838000 -2.421654000 H 2.456077000 3.751541000 -2.214063000 77 The TS2 with (tBuPCP)Pd(CH3) complex (B3LYP-D3/BS1, CPCM: Benzene) G298K=-1978.115668 Img. Freq.=-32.7875 cm-1 P 2.401628000 -0.000178000 0.006848000 P -2.259076000 0.343929000 -0.171418000 C 2.637400000 1.642990000 0.829379000 H 2.760157000 1.444494000 1.905573000 H 3.564217000 2.137606000 0.498946000 C 3.181572000 -1.245104000 1.215686000 C 4.567271000 -0.776908000 1.702996000 H 4.538912000 0.211817000 2.184757000 H 5.315523000 -0.747997000 0.900755000 H 4.927392000 -1.492806000 2.460500000 C 3.291784000 -2.646135000 0.589251000 H 3.725884000 -3.326255000 1.340831000 H 3.953093000 -2.669057000 -0.289277000 H 2.303085000 -3.053961000 0.338543000 C 2.204173000 -1.324032000 2.410948000 H 2.664602000 -1.946694000 3.196215000 H 1.260372000 -1.811437000 2.121103000 H 1.995295000 -0.339111000 2.858207000 C 3.260559000 0.108499000 -1.682902000 C 2.787325000 1.423371000 -2.338680000 H 3.180269000 1.466624000 -3.367944000 H 3.151830000 2.315442000 -1.808113000 H 1.689799000 1.485240000 -2.391343000 C 4.794157000 0.108212000 -1.587603000 H 5.217451000 0.288331000 -2.590161000 H 5.186815000 -0.856007000 -1.235575000 H 5.171421000 0.901984000 -0.924165000 C 2.780401000 -1.071367000 -2.552056000 H 1.689225000 -1.049084000 -2.695699000 H 3.045304000 -2.048228000 -2.125409000 H 3.251814000 -1.002246000 -3.546409000 C -2.250723000 2.177108000 -0.443546000 H -2.328644000 2.332313000 -1.532012000 H -3.127140000 2.668043000 0.007532000 C -2.961235000 0.079329000 1.577555000 C -2.219156000 1.040783000 2.529933000 H -2.557423000 0.834821000 3.558798000 H -2.426285000 2.100184000 2.318091000 H -1.130151000 0.892362000 2.498636000 C -4.469335000 0.370002000 1.653799000 H -5.063005000 -0.351832000 1.076965000 H -4.720879000 1.386740000 1.312582000 H -4.792192000 0.289326000 2.705277000 C -2.663464000 -1.365037000 2.019334000 H -3.065549000 -1.512786000 3.035910000 H -1.583017000 -1.569697000 2.057763000 H -3.101827000 -2.131364000 1.369235000 C -3.385154000 -0.333031000 -1.549917000 C -2.524416000 -0.328459000 -2.832055000 H -3.142895000 -0.659265000 -3.682674000 H -1.666255000 -1.010464000 -2.756172000 H -2.137396000 0.674085000 -3.075490000 C -3.848894000 -1.768345000 -1.241305000 H -4.597466000 -1.786111000 -0.436063000 H -3.041475000 -2.457572000 -0.949306000 H -4.335848000 -2.179300000 -2.141952000 C -4.617154000 0.565594000 -1.784843000 H -5.215847000 0.127891000 -2.601369000 H -4.347617000 1.586130000 -2.094534000 H -5.268016000 0.632823000 -0.904108000 Pd 0.070323000 -0.056763000 -0.242032000 O -0.002224000 -3.527936000 1.380978000 C -0.753671000 -3.529450000 0.377089000 C -0.178153000 -2.805852000 -0.868101000 H 0.403408000 -1.915653000 -0.502180000 H 0.610141000 -3.404507000 -1.351858000 H -0.927333000 -2.545939000 -1.621842000 O -1.893786000 -4.019875000 0.244861000 C 1.413959000 2.499991000 0.616418000 C 0.190304000 1.922445000 0.201089000 C 1.483191000 3.877198000 0.877712000 C -0.946418000 2.752431000 0.051260000 C 0.355320000 4.686876000 0.743183000 H 2.434756000 4.313634000 1.195913000 C -0.854034000 4.122971000 0.334670000 H 0.418769000 5.757457000 0.955339000 H -1.741976000 4.752878000 0.225734000 77 (tBuPCP)Pd(Acatate) (B3LYP-D3/BS1, CPCM: Benzene) G298K=-1978.173837 P 2.303098000 0.182450000 0.139157000 P -2.327837000 0.132283000 -0.052617000 C 2.395131000 1.996446000 0.523902000 H 2.447484000 2.081779000 1.621822000 H 3.313779000 2.462532000 0.133782000 C 3.154115000 -0.672205000 1.610334000 C 4.453866000 0.027973000 2.047728000 H 4.287735000 1.074487000 2.344389000 H 5.226654000 0.012082000 1.268424000 H 4.862858000 -0.497479000 2.927699000 C 3.434399000 -2.148014000 1.279059000 H 3.759789000 -2.666357000 2.197024000 H 4.237512000 -2.262759000 0.537154000 H 2.528096000 -2.649023000 0.910951000 C 2.129364000 -0.618718000 2.765874000 H 2.588724000 -1.046753000 3.673014000 H 1.230150000 -1.202739000 2.523085000 H 1.820382000 0.410644000 3.007877000 C 3.234065000 -0.030933000 -1.504874000 C 2.593634000 0.971196000 -2.489895000 H 3.048541000 0.828099000 -3.484172000 H 2.755825000 2.019210000 -2.197424000 H 1.509465000 0.809791000 -2.584416000 C 4.739368000 0.257378000 -1.388301000 H 5.187880000 0.239882000 -2.396207000 H 5.259384000 -0.503681000 -0.789107000 H 4.949916000 1.246948000 -0.953157000 C 3.006037000 -1.454471000 -2.047131000 H 1.938268000 -1.712972000 -2.099090000 H 3.505874000 -2.219634000 -1.438504000 H 3.429920000 -1.518691000 -3.063939000 C -2.499115000 1.824957000 -0.793444000 H -2.656386000 1.678739000 -1.874489000 H -3.389256000 2.356193000 -0.419411000 C -3.023905000 0.251638000 1.717386000 C -2.370018000 1.483873000 2.378912000 H -2.687192000 1.526885000 3.434387000 H -2.670358000 2.429038000 1.902851000 H -1.272019000 1.427759000 2.353493000 C -4.551521000 0.408087000 1.769586000 H -5.073212000 -0.494901000 1.423147000 H -4.904704000 1.264859000 1.174555000 H -4.861376000 0.583062000 2.814026000 C -2.589942000 -1.004392000 2.499985000 H -2.907992000 -0.900148000 3.551312000 H -1.498307000 -1.136767000 2.477675000 H -3.041920000 -1.924089000 2.106087000 C -3.359824000 -0.988808000 -1.187207000 C -2.539115000 -1.126955000 -2.488412000 H -3.105003000 -1.755017000 -3.197491000 H -1.565964000 -1.605564000 -2.306316000 H -2.371839000 -0.155009000 -2.979626000 C -3.517650000 -2.378772000 -0.545744000 H -4.210437000 -2.363790000 0.308536000 H -2.552637000 -2.780679000 -0.207388000 H -3.932287000 -3.076583000 -1.292156000 C -4.743140000 -0.401915000 -1.526732000 H -5.244723000 -1.075460000 -2.242532000 H -4.671927000 0.584835000 -2.008882000 H -5.398275000 -0.309839000 -0.651617000 Pd -0.007120000 -0.119658000 0.007311000 O 0.042712000 -2.201932000 0.483684000 C 0.077499000 -3.117863000 -0.420055000 C 0.170086000 -4.536497000 0.140629000 H 1.193133000 -4.708498000 0.514663000 H -0.514355000 -4.661552000 0.992956000 H -0.049671000 -5.277873000 -0.639081000 O 0.062183000 -2.930096000 -1.641811000 C 1.136471000 2.676906000 0.031994000 C 1.120613000 4.070801000 -0.125478000 C -0.032205000 1.907331000 -0.206196000 C -0.053502000 4.731558000 -0.492229000 H 2.035730000 4.644345000 0.052830000 C -1.220524000 2.598935000 -0.557825000 C -1.222170000 3.995161000 -0.695287000 H -0.060019000 5.818746000 -0.609715000 H -2.149912000 4.509207000 -0.965886000 42 (MePBP)Pd(CH3) complex (B3LYP-D3/BS1, CPCM: Benzene) G298K=-1453.477462 P 1.061179000 -2.254745000 0.000019000 P 1.046837000 2.262674000 0.000000000 N -1.367821000 -1.152880000 -0.000022000 N -1.375685000 1.148852000 -0.000056000 B -0.504220000 0.001021000 -0.000029000 C 3.727269000 -0.013028000 0.000008000 H 4.120438000 -0.547302000 -0.887743000 H 4.120473000 -0.547903000 0.887380000 H 4.195657000 0.988914000 0.000336000 C -0.829653000 -2.490941000 -0.000114000 H -1.135603000 -3.069834000 -0.891175000 H -1.135750000 -3.070023000 0.890774000 C 1.615209000 -3.258171000 -1.438985000 C 1.615102000 -3.258238000 1.439012000 C -2.691333000 -0.723490000 -0.000022000 C -3.890271000 -1.435556000 -0.000021000 H -3.887005000 -2.528566000 -0.000046000 C -5.096593000 -0.715178000 0.000017000 H -6.045032000 -1.259069000 0.000021000 C -5.101362000 0.685926000 0.000056000 H -6.053485000 1.223343000 0.000089000 C -3.899985000 1.414515000 0.000047000 H -3.904147000 2.507521000 0.000067000 C -2.696214000 0.710634000 0.000002000 C -0.845347000 2.490033000 0.000202000 H -1.154435000 3.067083000 0.891371000 H -1.154594000 3.067523000 -0.890626000 C 1.595590000 3.269685000 -1.438651000 C 1.596014000 3.269784000 1.438409000 Pd 1.539808000 0.006968000 0.000024000 H 2.714488000 -3.232418000 -1.479323000 H 1.271965000 -4.302140000 -1.363400000 H 1.223689000 -2.807593000 -2.362972000 H 1.223644000 -2.807688000 2.363038000 H 1.271817000 -4.302187000 1.363371000 H 2.714387000 -3.232525000 1.479306000 H 1.244654000 4.311087000 -1.362738000 H 2.695016000 3.252277000 -1.477450000 H 1.208098000 2.816771000 -2.363173000 H 1.245196000 4.311226000 1.362480000 H 1.208781000 2.817024000 2.363110000 H 2.695455000 3.252252000 1.476833000 45 The TS1_Inn for C-CO2 bond formation with (MePBP)Pd(CH3) complex (B3LYP-D3/BS1, CPCM: Benzene) G298K=-1641.904646 Img. Freq.=-334.5609 cm-1 P 0.596450000 -2.315237000 0.066522000 P 0.694039000 2.233977000 0.082723000 N -1.767869000 -1.121527000 -0.115606000 N -1.718814000 1.176353000 0.039107000 B -0.883273000 0.005916000 0.003506000 C 3.164931000 -0.263176000 1.357370000 H 3.515847000 -1.301816000 1.442413000 H 2.480173000 -0.047939000 2.206894000 H 4.017887000 0.415241000 1.500748000 C -1.284931000 -2.480246000 -0.057658000 H -1.558899000 -3.071036000 -0.950390000 H -1.668427000 -3.018581000 0.828500000 C 1.227703000 -3.081223000 -1.474169000 C 1.076154000 -3.502223000 1.381964000 C -3.080754000 -0.654188000 -0.134582000 C -4.294792000 -1.334512000 -0.218612000 H -4.318068000 -2.424700000 -0.291796000 C -5.481682000 -0.584033000 -0.204012000 H -6.442709000 -1.101038000 -0.268782000 C -5.452135000 0.813671000 -0.105807000 H -6.390446000 1.374484000 -0.094311000 C -4.234871000 1.508573000 -0.019203000 H -4.212380000 2.598177000 0.062278000 C -3.050514000 0.773249000 -0.035798000 C -1.165846000 2.488224000 0.282816000 H -1.382649000 2.850447000 1.305035000 H -1.535364000 3.247688000 -0.428737000 C 1.011871000 2.882239000 -1.604404000 C 1.494039000 3.454322000 1.190408000 Pd 1.111722000 -0.053030000 0.315724000 C 3.540293000 0.158276000 -0.762194000 O 3.723738000 1.341455000 -0.856159000 O 3.666821000 -0.911656000 -1.287289000 H 2.319364000 -2.957306000 -1.491567000 H 0.950465000 -4.145041000 -1.535874000 H 0.810934000 -2.535715000 -2.333540000 H 0.660311000 -3.168120000 2.343901000 H 0.720376000 -4.519661000 1.156407000 H 2.173678000 -3.507318000 1.459741000 H 0.756409000 3.951513000 -1.667990000 H 2.072967000 2.723969000 -1.837511000 H 0.399851000 2.311874000 -2.318415000 H 1.155900000 4.481154000 0.980495000 H 1.281392000 3.197453000 2.238473000 H 2.578703000 3.379085000 1.020871000 45 The TS1_Out for C-CO2 bond formation with (MePBP)Pd(CH3) complex (B3LYP-D3/BS1, CPCM: Benzene) G298K=-1641.895546 Img. Freq.=-604.7813 cm-1 P -0.023366000 2.520279000 0.000005000 P 0.916399000 -1.952069000 0.000019000 N -2.151552000 0.920807000 -0.000024000 N -1.675369000 -1.333298000 0.000020000 B -1.072011000 -0.028646000 0.000009000 C 3.212048000 0.731273000 0.000017000 H 3.538834000 1.771135000 0.000040000 H 3.153598000 0.214016000 -0.958536000 H 3.153611000 0.213968000 0.958544000 C -1.914283000 2.343197000 -0.000033000 H -2.337433000 2.841804000 0.891141000 H -2.337396000 2.841788000 -0.891233000 C 0.315883000 3.606850000 1.442754000 C 0.315942000 3.606843000 -1.442734000 C -3.356308000 0.221119000 -0.000025000 C -4.677230000 0.667310000 -0.000049000 H -4.903560000 1.736532000 -0.000072000 C -5.704333000 -0.290375000 -0.000041000 H -6.745846000 0.041744000 -0.000058000 C -5.414433000 -1.661577000 -0.000010000 H -6.232483000 -2.386738000 -0.000003000 C -4.087781000 -2.121960000 0.000013000 H -3.862172000 -3.191306000 0.000038000 C -3.060003000 -1.179740000 0.000005000 C -0.886098000 -2.541458000 0.000089000 H -1.074268000 -3.167480000 -0.891123000 H -1.074230000 -3.167346000 0.891404000 C 1.692825000 -2.787848000 1.436132000 C 1.692691000 -2.787770000 -1.436214000 Pd 0.902764000 0.389832000 0.000032000 C 4.971759000 -0.452479000 -0.000049000 O 5.923196000 0.266079000 -0.000004000 O 4.554171000 -1.582808000 -0.000106000 H 1.395528000 3.814882000 1.481683000 H -0.239903000 4.554907000 1.369806000 H 0.028585000 3.080625000 2.364970000 H 0.028686000 3.080613000 -2.364960000 H -0.239848000 4.554900000 -1.369815000 H 1.395588000 3.814878000 -1.481618000 H 2.767329000 -2.552622000 1.400164000 H 1.261350000 -2.398912000 2.369961000 H 1.549339000 -3.878691000 1.386304000 H 1.549226000 -3.878617000 -1.386423000 H 1.261117000 -2.398794000 -2.369980000 H 2.767196000 -2.552531000 -1.400342000 38 (MePCP)Pd(CH3) complex (B3LYP-D3/BS1, CPCM: Benzene) G298K=-1318.562422 P 2.274678000 -0.546467000 -0.028734000 C -0.018442000 1.191967000 -0.000732000 C -0.052486000 4.025437000 -0.000221000 C -1.208079000 1.908507000 -0.289474000 C 1.153796000 1.936612000 0.288496000 C -1.222893000 3.311602000 -0.277260000 C 1.134658000 3.339741000 0.276647000 C 3.482873000 -1.554520000 0.917837000 C 0.075383000 -3.045476000 -0.001299000 H -0.918100000 -3.526345000 -0.014882000 H 0.630321000 -3.415146000 -0.884471000 H 0.608496000 -3.411276000 0.896534000 C -3.009800000 -0.504012000 1.707828000 C -3.457059000 -1.634791000 -0.909222000 H -2.149725000 3.852336000 -0.495755000 H -0.065560000 5.119222000 -0.000071000 H 2.048153000 3.902598000 0.495402000 C -2.455881000 1.120011000 -0.646560000 H -3.387266000 1.596003000 -0.294968000 H -2.544818000 1.013796000 -1.743307000 C 2.421095000 1.179707000 0.646437000 H 3.340177000 1.679505000 0.295540000 H 2.511884000 1.076179000 1.743297000 P -2.263750000 -0.601417000 0.029559000 Pd 0.009017000 -0.915870000 -0.002332000 C 3.025675000 -0.436182000 -1.703573000 H 4.075552000 -0.106983000 -1.647568000 H 2.973299000 -1.419232000 -2.194882000 H 2.445234000 0.284149000 -2.298357000 H 3.484568000 -2.578612000 0.514868000 H 4.499267000 -1.134443000 0.853744000 H 3.168529000 -1.598580000 1.971093000 H -4.481228000 -1.235598000 -0.835631000 H -3.151025000 -1.670141000 -1.965269000 H -3.435219000 -2.659458000 -0.508620000 H -4.066774000 -0.197781000 1.654731000 H -2.934526000 -1.484156000 2.201867000 H -2.442968000 0.230645000 2.298160000 41 The TS1_Inn for C-CO2 bond formation with (MePCP)Pd(CH3) complex (B3LYP-D3/BS1, CPCM: Benzene) G298K=-1506.980213 Img. Freq.=-411.0224 cm-1 P -1.144153000 -1.948114000 0.177431000 C 1.359831000 -0.635564000 -0.050358000 C 3.871037000 -1.848219000 -0.486418000 C 2.450294000 0.122845000 -0.544532000 C 1.550615000 -2.015041000 0.216811000 C 3.697461000 -0.486285000 -0.747716000 C 2.799858000 -2.610458000 -0.012301000 C -2.573997000 -2.539906000 1.148992000 C -2.361852000 1.320935000 1.077590000 H -2.242688000 2.409905000 1.143076000 H -3.421148000 1.058212000 1.195960000 C 1.649125000 2.673218000 1.778873000 C 0.221628000 3.737145000 -0.516142000 H 4.536693000 0.108035000 -1.122098000 H 4.844161000 -2.317687000 -0.654885000 H 2.937068000 -3.677418000 0.188764000 C 2.233133000 1.588053000 -0.863148000 H 3.142508000 2.199144000 -0.740039000 H 1.891423000 1.711105000 -1.906622000 C 0.383042000 -2.821081000 0.753553000 H 0.409297000 -3.878651000 0.443358000 H 0.368073000 -2.800513000 1.858031000 P 0.841947000 2.177198000 0.206877000 Pd -0.461049000 0.255743000 0.294535000 C -1.426700000 -2.581790000 -1.516185000 H -1.627999000 -3.664495000 -1.496836000 H -2.278669000 -2.037780000 -1.945183000 H -0.528301000 -2.382130000 -2.117920000 H -3.454819000 -2.000429000 0.770158000 H -2.719966000 -3.625549000 1.036361000 H -2.429027000 -2.290953000 2.210438000 H 1.046965000 4.441613000 -0.703903000 H -0.319429000 3.501438000 -1.442143000 H -0.495445000 4.190402000 0.184596000 H 2.361941000 3.496626000 1.613460000 H 0.881847000 2.992134000 2.500207000 H 2.180223000 1.802456000 2.190730000 H -1.863897000 0.847090000 1.952182000 C -2.650570000 0.981093000 -0.907706000 O -3.305489000 -0.029794000 -1.040029000 O -2.281373000 1.955711000 -1.517324000 41 The TS1_Out for C-CO2 bond formation with (MePCP)Pd(CH3) complex (B3LYP-D3/BS1, CPCM: Benzene) G298K=-1506.973149 Img. Freq.=-632.9094 cm-1 P -0.885063000 -1.934771000 0.129777000 C 1.654803000 -0.526366000 -0.058396000 C 4.241920000 -1.644630000 -0.299102000 C 2.767662000 0.283651000 -0.403192000 C 1.867831000 -1.912302000 0.154605000 C 4.049352000 -0.276624000 -0.508275000 C 3.153701000 -2.459137000 0.023619000 C -2.133119000 -2.547456000 1.322095000 C -2.359967000 1.169136000 0.138934000 H -2.385021000 2.247864000 0.292865000 H -2.492426000 0.526381000 1.008890000 C 1.433006000 2.870826000 1.756714000 C 0.399037000 3.771602000 -0.794178000 H 4.901177000 0.359717000 -0.768100000 H 5.242006000 -2.077414000 -0.390623000 H 3.306150000 -3.530978000 0.184844000 C 2.546915000 1.753998000 -0.701239000 H 3.388086000 2.392110000 -0.382422000 H 2.418032000 1.909929000 -1.787699000 C 0.702672000 -2.792592000 0.560007000 H 0.751193000 -3.800183000 0.114182000 H 0.691403000 -2.931577000 1.656334000 P 0.952417000 2.264674000 0.091651000 Pd -0.239441000 0.296055000 0.091586000 C -1.440953000 -2.621295000 -1.475252000 H -1.565827000 -3.713933000 -1.413848000 H -2.405445000 -2.148811000 -1.715276000 H -0.705434000 -2.374548000 -2.254490000 H -3.102225000 -2.109960000 1.040870000 H -2.195767000 -3.646986000 1.292728000 H -1.862966000 -2.221913000 2.337511000 H 1.176779000 4.551470000 -0.774639000 H 0.163556000 3.512593000 -1.836978000 H -0.514542000 4.155823000 -0.316383000 H 2.125083000 3.724227000 1.678793000 H 0.533994000 3.175291000 2.312819000 H 1.920940000 2.048355000 2.299823000 H -2.216789000 0.800270000 -0.880166000 C -4.237383000 0.554731000 -0.286250000 O -4.146056000 -0.633145000 -0.494908000 O -4.984050000 1.488636000 -0.231835000 78 (tBuPBP)Ni(CH3) complex (B3LYP-D3/BS1, CPCM: Benzene) G298K=-3304.827966 P -2.151938000 -0.585609000 -0.067339000 P 2.162653000 -0.545729000 0.052276000 N -1.145445000 1.818775000 -0.277226000 N 1.095071000 1.844967000 0.164805000 B -0.013814000 0.949562000 -0.058637000 C 0.022780000 -3.027237000 -0.163682000 H -0.376470000 -3.379614000 -1.136727000 H -0.604770000 -3.517782000 0.604823000 H 1.010748000 -3.511528000 -0.083242000 C -2.440658000 1.240374000 -0.512984000 H -2.751499000 1.330842000 -1.567585000 H -3.235530000 1.696551000 0.102062000 C -3.256738000 -1.484365000 -1.336466000 C -4.611736000 -0.805217000 -1.609500000 H -4.503031000 0.224598000 -1.980068000 H -5.261503000 -0.783702000 -0.725217000 H -5.143281000 -1.373434000 -2.392646000 C -3.495455000 -2.941883000 -0.904915000 H -3.968012000 -3.492904000 -1.736218000 H -4.176649000 -3.008165000 -0.043610000 H -2.557981000 -3.453060000 -0.650470000 C -2.414434000 -1.470957000 -2.631361000 H -2.957757000 -1.998936000 -3.433545000 H -1.445429000 -1.966183000 -2.476743000 H -2.215290000 -0.445988000 -2.984244000 C -2.846954000 -0.691187000 1.712100000 C -2.135906000 0.403986000 2.537424000 H -2.455728000 0.319969000 3.589981000 H -2.376850000 1.421900000 2.198467000 H -1.042561000 0.285831000 2.501861000 C -4.366793000 -0.490030000 1.801618000 H -4.668767000 -0.464015000 2.862905000 H -4.921243000 -1.311762000 1.326742000 H -4.693640000 0.457482000 1.345942000 C -2.458459000 -2.055027000 2.313558000 H -1.369333000 -2.198116000 2.284856000 H -2.919013000 -2.899419000 1.783684000 H -2.790759000 -2.096487000 3.364986000 C -0.746713000 3.143974000 -0.183428000 C -1.457815000 4.337097000 -0.310447000 H -2.528363000 4.324835000 -0.530883000 C -0.765086000 5.549070000 -0.148103000 H -1.308187000 6.493251000 -0.243391000 C 0.607854000 5.565057000 0.132538000 H 1.123300000 6.521552000 0.254796000 C 1.335516000 4.369609000 0.261115000 H 2.405815000 4.382299000 0.482724000 C 0.659191000 3.160387000 0.101104000 C 2.390020000 1.298571000 0.466672000 H 2.647147000 1.420568000 1.532049000 H 3.203342000 1.758793000 -0.120327000 C 2.988613000 -0.692775000 -1.662163000 C 2.285285000 0.337719000 -2.573099000 H 2.679337000 0.236322000 -3.598589000 H 2.452764000 1.376862000 -2.254448000 H 1.198464000 0.165953000 -2.605135000 C 4.500603000 -0.422886000 -1.652431000 H 5.054476000 -1.190410000 -1.093309000 H 4.749823000 0.561768000 -1.227242000 H 4.880603000 -0.436788000 -2.688614000 C 2.703240000 -2.095099000 -2.233202000 H 3.085349000 -2.149338000 -3.267032000 H 1.624009000 -2.301711000 -2.247119000 H 3.188257000 -2.894201000 -1.657554000 C 3.185035000 -1.391650000 1.428794000 C 2.208303000 -1.450224000 2.622915000 H 2.705606000 -1.914049000 3.491935000 H 1.315983000 -2.042453000 2.368571000 H 1.869122000 -0.446498000 2.927877000 C 3.581677000 -2.825717000 1.037936000 H 4.345526000 -2.842863000 0.246909000 H 2.717792000 -3.414508000 0.703942000 H 4.013280000 -3.331350000 1.918714000 C 4.455361000 -0.622164000 1.839087000 H 4.972655000 -1.186687000 2.634106000 H 4.235931000 0.374481000 2.247564000 H 5.164063000 -0.503309000 1.008386000 Ni 0.011744000 -0.994967000 -0.061869000 81 The TS1_Out for C-CO2 bond formation with (tBuPBP)Ni(CH3) complex (B3LYP-D3/BS1, CPCM: Benzene) G298K=-3493.244354 Img. Freq.=-604.0527 cm-1 P 1.096592000 1.860703000 -0.194183000 P -0.792879000 -2.063115000 -0.056148000 N -1.511319000 1.956208000 -0.242918000 N -2.451699000 -0.064788000 0.263150000 B -1.203127000 0.559259000 -0.084212000 C 2.420483000 -1.241775000 -0.460196000 H 2.944872000 -0.598418000 -1.159043000 H 2.216337000 -2.261499000 -0.762923000 H 2.288025000 -0.936598000 0.583001000 C -0.455791000 2.888382000 -0.536543000 H -0.495033000 3.794473000 0.091614000 H -0.468587000 3.216829000 -1.589232000 C 1.567692000 2.356930000 1.589204000 C 2.338098000 2.513096000 -1.485687000 C -2.861231000 2.165180000 0.009312000 C -3.635156000 3.325312000 -0.001395000 H -3.187303000 4.290753000 -0.250174000 C -4.999521000 3.218979000 0.314773000 H -5.621065000 4.118347000 0.312696000 C -5.574912000 1.980425000 0.631153000 H -6.639502000 1.925768000 0.873722000 C -4.805473000 0.805458000 0.643706000 H -5.253332000 -0.159548000 0.894196000 C -3.449532000 0.899315000 0.331702000 C -2.489345000 -1.472826000 0.552426000 H -3.315021000 -1.998952000 0.044022000 H -2.592912000 -1.666308000 1.633022000 C -0.316292000 -3.382497000 1.241155000 C -1.183556000 -2.807817000 -1.769271000 C 4.163720000 -1.735982000 0.538534000 O 4.879202000 -0.770392000 0.504669000 O 4.033829000 -2.860184000 0.940102000 C -1.926713000 -1.713237000 -2.566558000 H -1.332651000 -0.788647000 -2.628723000 H -2.099139000 -2.077394000 -3.593231000 H -2.906229000 -1.458366000 -2.136956000 C -2.048689000 -4.075597000 -1.707041000 H -2.313939000 -4.384029000 -2.732661000 H -1.516756000 -4.917502000 -1.241885000 H -2.990918000 -3.915380000 -1.160602000 C 0.138559000 -3.105427000 -2.502702000 H -0.088377000 -3.486935000 -3.512506000 H 0.745974000 -2.195010000 -2.607456000 H 0.748624000 -3.862366000 -1.991680000 C -1.514296000 -4.234495000 1.706179000 H -1.956719000 -4.823226000 0.892225000 H -1.163793000 -4.946849000 2.472131000 H -2.310775000 -3.634904000 2.169404000 C 0.795485000 -4.318560000 0.733835000 H 1.072697000 -5.005871000 1.550882000 H 0.463756000 -4.939295000 -0.111014000 H 1.711977000 -3.781720000 0.455606000 C 0.227101000 -2.570687000 2.437494000 H 1.156679000 -2.046227000 2.173885000 H -0.496910000 -1.824810000 2.804040000 H 0.454326000 -3.254332000 3.272379000 C 0.303714000 2.207983000 2.464130000 H -0.115746000 1.192551000 2.404591000 H 0.579050000 2.400078000 3.514673000 H -0.490787000 2.919339000 2.195781000 C 2.625793000 1.366077000 2.115058000 H 2.948550000 1.682731000 3.120930000 H 2.200986000 0.355787000 2.212970000 H 3.518949000 1.285178000 1.482996000 C 2.088249000 3.798383000 1.701069000 H 2.244550000 4.044113000 2.765145000 H 3.052149000 3.934057000 1.191778000 H 1.374225000 4.533482000 1.298390000 C 3.785561000 2.159537000 -1.097184000 H 4.446338000 2.376005000 -1.953666000 H 4.141340000 2.769308000 -0.254059000 H 3.930047000 1.105457000 -0.825211000 C 2.239940000 4.032207000 -1.728316000 H 2.479933000 4.621896000 -0.834492000 H 2.967413000 4.311888000 -2.509441000 H 1.248461000 4.341725000 -2.089704000 C 1.952430000 1.774307000 -2.786392000 H 2.041270000 0.684252000 -2.675073000 H 0.916721000 1.993073000 -3.093939000 H 2.617549000 2.096446000 -3.605073000 Ni 0.515129000 -0.285029000 -0.243778000 81 The TS1_Inn for C-CO2 bond formation with (tBuPBP)Ni(CH3) complex (B3LYP-D3/BS1, CPCM: Benzene) G298K=-3493.237364 Img. Freq.=-356.676 cm-1 P -2.166236000 -0.669941000 0.033424000 P 2.221186000 -0.013972000 -0.173846000 N -1.373962000 1.729978000 0.643555000 N 0.746783000 2.132184000 -0.088091000 B -0.157283000 1.063736000 0.249831000 C 0.193925000 -2.749015000 -1.074482000 H -0.489898000 -3.601968000 -0.958533000 H -0.292533000 -2.095006000 -1.823211000 H 1.126157000 -3.115207000 -1.515097000 C -2.559313000 0.957686000 0.906102000 H -3.467681000 1.436981000 0.514429000 H -2.714952000 0.784509000 1.981930000 C -2.846394000 -0.350459000 -1.752157000 C -3.261322000 -1.923749000 0.978883000 C -1.214285000 3.105433000 0.536422000 C -2.092649000 4.160821000 0.781139000 H -3.108765000 3.969815000 1.135500000 C -1.635944000 5.471292000 0.562985000 H -2.310897000 6.310941000 0.749216000 C -0.331057000 5.718191000 0.114370000 H -0.000677000 6.747931000 -0.045916000 C 0.561229000 4.662378000 -0.135660000 H 1.576836000 4.853804000 -0.491238000 C 0.116453000 3.357756000 0.075640000 C 2.061386000 1.825318000 -0.574912000 H 2.852177000 2.421056000 -0.089130000 H 2.149927000 1.985129000 -1.662980000 C 3.356382000 -0.619016000 -1.586719000 C 3.137110000 0.046977000 1.515781000 C 0.853235000 -3.163571000 0.959461000 O 0.112555000 -2.734639000 1.801121000 O 1.786915000 -3.858986000 0.710808000 C 2.315517000 0.961193000 2.450806000 H 1.275262000 0.615116000 2.541512000 H 2.770956000 0.932007000 3.454882000 H 2.299342000 2.010986000 2.125190000 C 4.569111000 0.596148000 1.406637000 H 4.973035000 0.737945000 2.423345000 H 5.239372000 -0.103261000 0.888126000 H 4.619236000 1.570934000 0.898597000 C 3.178687000 -1.352266000 2.156038000 H 3.787422000 -1.302476000 3.074693000 H 2.173588000 -1.681087000 2.446300000 H 3.614192000 -2.119276000 1.504759000 C 4.516835000 0.338368000 -1.924219000 H 5.245263000 0.435181000 -1.111463000 H 5.057159000 -0.064999000 -2.797816000 H 4.171201000 1.345659000 -2.200153000 C 3.918975000 -2.010853000 -1.250542000 H 4.388910000 -2.440052000 -2.151809000 H 4.696260000 -1.955769000 -0.473603000 H 3.143689000 -2.706698000 -0.903447000 C 2.440522000 -0.711300000 -2.827229000 H 1.627251000 -1.430612000 -2.685293000 H 1.993632000 0.261675000 -3.087399000 H 3.039185000 -1.038949000 -3.693786000 C -1.754907000 0.416890000 -2.532193000 H -0.819047000 -0.153125000 -2.614589000 H -2.120776000 0.616673000 -3.553853000 H -1.515723000 1.383081000 -2.065795000 C -3.106624000 -1.691843000 -2.463665000 H -3.328605000 -1.494449000 -3.526040000 H -2.235602000 -2.360910000 -2.428385000 H -3.972181000 -2.223857000 -2.044963000 C -4.130177000 0.500265000 -1.795638000 H -4.479081000 0.556950000 -2.840688000 H -4.950964000 0.082132000 -1.199860000 H -3.952037000 1.534395000 -1.466178000 C -2.938940000 -3.362288000 0.533705000 H -3.584105000 -4.059222000 1.095265000 H -3.121099000 -3.535000000 -0.534232000 H -1.896551000 -3.613594000 0.757934000 C -4.764975000 -1.645945000 0.814315000 H -5.120036000 -1.841956000 -0.207061000 H -5.326758000 -2.315486000 1.488175000 H -5.032942000 -0.612449000 1.084619000 C -2.892485000 -1.799287000 2.475623000 H -1.806670000 -1.831413000 2.632109000 H -3.300477000 -0.886694000 2.934077000 H -3.332999000 -2.653496000 3.016518000 Ni 0.124139000 -0.826313000 -0.064433000 81 (tBuPBP)Ni(Acatate) (B3LYP-D3/BS1, CPCM: Benzene) G298K=-3493.325557 P 2.097775000 -0.740779000 0.045144000 P -2.167313000 0.299421000 -0.024423000 N 1.657122000 1.833183000 0.037260000 N -0.550270000 2.365193000 -0.226982000 B 0.346098000 1.245406000 -0.099102000 C 2.800876000 0.996982000 0.289041000 H 3.176799000 1.114565000 1.319245000 H 3.645182000 1.199352000 -0.392118000 C 2.835736000 -1.730756000 1.490025000 C 4.311161000 -1.407072000 1.784675000 H 4.468047000 -0.352542000 2.055891000 H 4.972162000 -1.645971000 0.940795000 H 4.643273000 -2.013244000 2.645010000 C 2.672680000 -3.240316000 1.242509000 H 2.920524000 -3.783833000 2.170165000 H 3.351169000 -3.606947000 0.458517000 H 1.636377000 -3.480521000 0.970136000 C 1.959809000 -1.334772000 2.699796000 H 2.347224000 -1.824263000 3.609510000 H 0.920195000 -1.658544000 2.544276000 H 1.961556000 -0.247411000 2.881334000 C 2.752558000 -1.270599000 -1.658105000 C 2.299184000 -0.172108000 -2.645153000 H 2.595685000 -0.466433000 -3.665773000 H 2.753149000 0.808175000 -2.437363000 H 1.205276000 -0.050782000 -2.629619000 C 4.279620000 -1.423871000 -1.711448000 H 4.588547000 -1.625043000 -2.751526000 H 4.628860000 -2.268329000 -1.099939000 H 4.808471000 -0.515474000 -1.382337000 C 2.065582000 -2.587207000 -2.068760000 H 0.969209000 -2.514090000 -2.019855000 H 2.371459000 -3.434976000 -1.441980000 H 2.348511000 -2.827613000 -3.107870000 C 1.552565000 3.217650000 0.007890000 C 2.515638000 4.219980000 0.119102000 H 3.569576000 3.966144000 0.258479000 C 2.095766000 5.558823000 0.047976000 H 2.837334000 6.357724000 0.132468000 C 0.744078000 5.884550000 -0.129196000 H 0.444007000 6.934513000 -0.182558000 C -0.234804000 4.882915000 -0.239716000 H -1.288815000 5.137165000 -0.377561000 C 0.170670000 3.550510000 -0.167488000 C -1.963805000 2.150196000 -0.377338000 H -2.307012000 2.382507000 -1.398205000 H -2.564597000 2.763130000 0.315995000 C -2.907502000 0.255454000 1.729924000 C -1.895530000 1.001316000 2.628142000 H -2.244047000 0.959974000 3.673830000 H -1.781025000 2.061535000 2.357409000 H -0.900526000 0.532418000 2.581354000 C -4.289780000 0.914263000 1.845162000 H -5.058684000 0.355387000 1.292730000 H -4.294430000 1.955551000 1.486732000 H -4.597491000 0.931405000 2.904897000 C -2.976586000 -1.210300000 2.204596000 H -3.230278000 -1.228616000 3.278213000 H -2.016656000 -1.725612000 2.057010000 H -3.748386000 -1.784044000 1.674616000 C -3.399047000 -0.244384000 -1.371566000 C -2.514897000 -0.424607000 -2.625004000 H -3.150835000 -0.693328000 -3.485866000 H -1.785501000 -1.232281000 -2.462962000 H -1.975005000 0.500556000 -2.887451000 C -4.052445000 -1.591543000 -1.019798000 H -4.761476000 -1.500563000 -0.184088000 H -3.306505000 -2.362294000 -0.791489000 H -4.623542000 -1.944293000 -1.895376000 C -4.507104000 0.788674000 -1.652496000 H -5.167936000 0.388858000 -2.440483000 H -4.114847000 1.746597000 -2.023061000 H -5.132476000 0.991163000 -0.772408000 O -0.461461000 -2.464260000 0.530065000 C -0.948819000 -3.377973000 -0.232216000 C -1.247206000 -4.690586000 0.487148000 H -0.346150000 -5.053539000 1.006289000 H -2.014460000 -4.516034000 1.258969000 H -1.602484000 -5.451382000 -0.220157000 O -1.183438000 -3.259527000 -1.440518000 Ni -0.112000000 -0.599109000 0.032369000 3 Carbon dioxide (ωB97XD/BS1, CPCM: Benzene) G298K=-188.390857 C 0.000000000 0.000000000 0.000000000 O 0.000000000 0.000000000 1.158552000 O 0.000000000 0.000000000 -1.158552000 78 (tBuPBP)Pd(CH3) complex (ωB97XD/BS1, CPCM: Benzene) G298K=-1924.173478 P -2.262597000 -0.484538000 -0.054134000 P 2.263884000 -0.489273000 0.059368000 N -1.129871000 1.889411000 -0.209850000 N 1.124871000 1.890930000 0.173024000 B -0.002527000 1.020455000 -0.011092000 C -0.042885000 -3.191056000 -0.168821000 H -0.433758000 -3.504377000 -1.157677000 H -0.711107000 -3.652783000 0.582654000 H 0.932686000 -3.696824000 -0.064990000 C -2.436359000 1.350560000 -0.461709000 H -2.732583000 1.470948000 -1.517693000 H -3.221199000 1.827541000 0.150623000 C -3.342774000 -1.310538000 -1.361432000 C -4.671952000 -0.595305000 -1.642617000 H -4.528878000 0.440370000 -1.983437000 H -5.338826000 -0.579740000 -0.771876000 H -5.199386000 -1.129540000 -2.450079000 C -3.609529000 -2.768058000 -0.964100000 H -4.052563000 -3.301770000 -1.820779000 H -4.322787000 -2.842244000 -0.130207000 H -2.681477000 -3.286147000 -0.683133000 C -2.483860000 -1.295004000 -2.639454000 H -3.045158000 -1.764906000 -3.463393000 H -1.546127000 -1.849874000 -2.491478000 H -2.226499000 -0.271373000 -2.954541000 C -2.996112000 -0.610652000 1.686369000 C -2.278754000 0.441570000 2.552082000 H -2.622396000 0.336619000 3.593819000 H -2.492422000 1.472961000 2.235938000 H -1.187939000 0.299797000 2.536077000 C -4.507520000 -0.365049000 1.744241000 H -4.829825000 -0.333887000 2.797926000 H -5.074513000 -1.169729000 1.255495000 H -4.796869000 0.592784000 1.285250000 C -2.667761000 -1.995826000 2.264523000 H -1.583224000 -2.175949000 2.266083000 H -3.138852000 -2.812013000 1.701676000 H -3.033968000 -2.049071000 3.302831000 C -0.704808000 3.207836000 -0.148594000 C -1.400412000 4.404086000 -0.281684000 H -2.475480000 4.404977000 -0.477093000 C -0.689203000 5.605348000 -0.159294000 H -1.220796000 6.554577000 -0.260049000 C 0.684764000 5.606350000 0.088397000 H 1.216483000 6.556353000 0.180853000 C 1.395794000 4.406104000 0.221335000 H 2.470877000 4.408571000 0.416657000 C 0.699937000 3.208842000 0.099182000 C 2.429406000 1.355147000 0.438794000 H 2.718466000 1.494736000 1.493911000 H 3.217215000 1.823348000 -0.176180000 C 3.076475000 -0.657289000 -1.639184000 C 2.366307000 0.350891000 -2.561604000 H 2.754506000 0.231071000 -3.585903000 H 2.535518000 1.395982000 -2.263594000 H 1.280070000 0.176094000 -2.584822000 C 4.582784000 -0.377005000 -1.643100000 H 5.146352000 -1.148177000 -1.099091000 H 4.830433000 0.604446000 -1.210164000 H 4.950173000 -0.378382000 -2.682433000 C 2.802258000 -2.067961000 -2.183627000 H 3.176732000 -2.133650000 -3.218237000 H 1.725371000 -2.290153000 -2.183884000 H 3.302791000 -2.850224000 -1.598593000 C 3.279958000 -1.284576000 1.438057000 C 2.344992000 -1.269410000 2.661174000 H 2.865258000 -1.708510000 3.527993000 H 1.433011000 -1.853246000 2.464626000 H 2.039810000 -0.247717000 2.937691000 C 3.603206000 -2.741096000 1.084047000 H 4.364455000 -2.813823000 0.293843000 H 2.705518000 -3.286011000 0.760909000 H 4.007533000 -3.248364000 1.975155000 C 4.579591000 -0.543210000 1.784057000 H 5.085707000 -1.077868000 2.604719000 H 4.400974000 0.483563000 2.133542000 H 5.280198000 -0.500542000 0.940650000 Pd 0.000077000 -1.016599000 -0.035154000 81 The TS1_Out for C-CO2 bond formation with (tBuPBP)Pd(CH3) complex (ωB97XD/BS1, CPCM: Benzene) G298K=-2112.526823 Img. Freq.=-669.4098 cm-1 P -1.368509000 1.888401000 -0.012934000 P 1.470619000 -1.690809000 0.118624000 N -2.491144000 -0.486079000 -0.215955000 N -1.099441000 -2.256154000 0.193874000 B -1.122898000 -0.832844000 0.030589000 C 2.240165000 1.859661000 0.267621000 H 1.829682000 2.811410000 0.590279000 H 2.326192000 1.651091000 -0.802630000 H 2.780344000 1.266491000 1.001717000 C -2.881209000 0.869212000 -0.482716000 H -3.768704000 1.179911000 0.094422000 H -3.118575000 1.021297000 -1.548750000 C -1.815082000 2.596098000 1.680082000 C -1.291479000 3.192778000 -1.374712000 C -3.255367000 -1.645496000 -0.213725000 C -4.616191000 -1.845291000 -0.414973000 H -5.279843000 -1.002657000 -0.622971000 C -5.112081000 -3.153230000 -0.345289000 H -6.178995000 -3.329779000 -0.500211000 C -4.264984000 -4.231819000 -0.081812000 H -4.677145000 -5.242309000 -0.031476000 C -2.892387000 -4.040477000 0.120153000 H -2.231548000 -4.885327000 0.328044000 C -2.390565000 -2.745949000 0.050091000 C 0.123049000 -2.954761000 0.473862000 H 0.248749000 -3.859048000 -0.145845000 H 0.179544000 -3.272210000 1.528418000 C 2.770402000 -2.055891000 1.436074000 C 2.053768000 -2.129692000 -1.624012000 Pd 0.449159000 0.422755000 0.127070000 C 4.121701000 2.612748000 -0.243958000 O 4.018217000 3.798320000 -0.292614000 O 4.831103000 1.658871000 -0.372905000 C 0.802510000 -2.224601000 -2.515954000 H 0.207246000 -1.300036000 -2.480534000 H 1.124529000 -2.380809000 -3.557934000 H 0.146177000 -3.064181000 -2.244041000 C 2.820085000 -3.455283000 -1.696951000 H 3.022637000 -3.696416000 -2.752954000 H 3.790292000 -3.403196000 -1.184279000 H 2.246444000 -4.294762000 -1.274907000 C 2.927399000 -0.980897000 -2.154669000 H 3.313411000 -1.253164000 -3.150131000 H 2.336643000 -0.060163000 -2.266119000 H 3.784649000 -0.743766000 -1.511886000 C 2.971957000 -3.555016000 1.707897000 H 3.333551000 -4.101071000 0.827970000 H 3.730288000 -3.670313000 2.499303000 H 2.056756000 -4.047075000 2.067036000 C 4.116151000 -1.423382000 1.057547000 H 4.790132000 -1.472890000 1.927950000 H 4.607118000 -1.967247000 0.237857000 H 4.037496000 -0.368703000 0.758107000 C 2.235371000 -1.385985000 2.715007000 H 2.140879000 -0.297415000 2.591792000 H 1.248377000 -1.778204000 3.007672000 H 2.930527000 -1.580979000 3.547240000 C -2.240877000 1.403903000 2.556781000 H -1.455436000 0.634454000 2.601619000 H -2.421331000 1.765171000 3.581708000 H -3.167339000 0.925218000 2.207852000 C -0.559346000 3.218771000 2.309677000 H -0.809533000 3.591528000 3.315908000 H 0.245970000 2.476642000 2.407861000 H -0.167342000 4.064708000 1.729835000 C -2.946835000 3.628089000 1.637776000 H -3.233299000 3.893564000 2.668265000 H -2.637828000 4.556647000 1.137484000 H -3.848313000 3.244694000 1.135676000 C -0.336420000 4.327058000 -0.981863000 H -0.188888000 4.987390000 -1.851427000 H -0.742574000 4.946506000 -0.169256000 H 0.651486000 3.952225000 -0.680569000 C -2.658652000 3.783964000 -1.750794000 H -3.124320000 4.334050000 -0.924000000 H -2.519148000 4.495950000 -2.580394000 H -3.369275000 3.021090000 -2.099518000 C -0.709290000 2.454701000 -2.594457000 H 0.306069000 2.084473000 -2.390236000 H -1.327936000 1.596106000 -2.899335000 H -0.657507000 3.147488000 -3.449496000 81 The TS1_Inn for C-CO2 bond formation with (tBuPBP)Pd(CH3) complex (ωB97XD/BS1, CPCM: Benzene) G298K=-2112.520358 Img. Freq.=-484.7612 cm-1 P -2.272589000 0.129264000 0.224871000 P 2.250114000 -0.633317000 0.080408000 N -0.720528000 2.197773000 -0.320471000 N 1.487213000 1.737291000 -0.700200000 B 0.224337000 1.122656000 -0.395035000 C -0.416413000 -3.116906000 0.324644000 H -1.396462000 -3.469533000 0.668471000 H 0.136774000 -2.750215000 1.212770000 H 0.165972000 -3.996146000 0.003870000 C -2.121629000 1.972116000 -0.120409000 H -2.700647000 2.231467000 -1.021331000 H -2.535049000 2.570285000 0.709426000 C -3.712451000 -0.362332000 -0.895672000 C -2.734668000 0.053846000 2.060212000 C -0.063275000 3.396522000 -0.564023000 C -0.533087000 4.703993000 -0.603292000 H -1.590164000 4.923770000 -0.436055000 C 0.385191000 5.730142000 -0.858983000 H 0.036021000 6.764782000 -0.891943000 C 1.736661000 5.450472000 -1.072583000 H 2.432694000 6.268988000 -1.270302000 C 2.216111000 4.134860000 -1.043996000 H 3.271985000 3.917318000 -1.221452000 C 1.310958000 3.110492000 -0.790947000 C 2.704908000 0.978637000 -0.750641000 H 3.535248000 1.480536000 -0.225260000 H 3.037094000 0.787873000 -1.784981000 C 3.412658000 -1.886528000 -0.718984000 C 2.709370000 -0.314476000 1.900500000 Pd -0.126306000 -0.836003000 -0.098958000 C -0.984765000 -3.080634000 -1.778998000 O -0.310181000 -2.369313000 -2.458896000 O -1.845921000 -3.891945000 -1.719516000 C 2.194012000 1.079149000 2.301415000 H 1.128030000 1.213268000 2.079359000 H 2.330681000 1.203444000 3.387505000 H 2.745194000 1.891537000 1.806378000 C 4.216444000 -0.353426000 2.178723000 H 4.391978000 -0.051493000 3.223924000 H 4.640575000 -1.358880000 2.056773000 H 4.776708000 0.344960000 1.539199000 C 1.997307000 -1.360951000 2.771163000 H 2.274122000 -1.207204000 3.826563000 H 0.904745000 -1.266783000 2.691193000 H 2.265826000 -2.391789000 2.501404000 C 4.865092000 -1.405853000 -0.860774000 H 5.385638000 -1.303057000 0.097360000 H 5.420505000 -2.149577000 -1.455164000 H 4.937654000 -0.448729000 -1.398469000 C 3.359733000 -3.202007000 0.068777000 H 3.895698000 -3.983278000 -0.493752000 H 3.842229000 -3.120007000 1.053489000 H 2.324778000 -3.543469000 0.213989000 C 2.846849000 -2.128166000 -2.127465000 H 1.810882000 -2.485050000 -2.100990000 H 2.866789000 -1.216190000 -2.744210000 H 3.468692000 -2.881388000 -2.637642000 C -3.135706000 -0.326996000 -2.322668000 H -2.256976000 -0.973203000 -2.438324000 H -3.907393000 -0.665480000 -3.032064000 H -2.840192000 0.691242000 -2.620844000 C -4.171736000 -1.784480000 -0.551394000 H -4.855752000 -2.142899000 -1.337240000 H -3.335470000 -2.493989000 -0.496679000 H -4.725628000 -1.810141000 0.398501000 C -4.922818000 0.584020000 -0.845740000 H -5.643360000 0.262008000 -1.615021000 H -5.445862000 0.560563000 0.116758000 H -4.662038000 1.628143000 -1.070752000 C -2.663674000 -1.401492000 2.546013000 H -2.904090000 -1.431595000 3.621099000 H -3.372706000 -2.059170000 2.027436000 H -1.657853000 -1.821294000 2.410430000 C -4.116615000 0.636483000 2.374967000 H -4.925708000 -0.005938000 2.001818000 H -4.236206000 0.706479000 3.468256000 H -4.255684000 1.647869000 1.963811000 C -1.662130000 0.850875000 2.820073000 H -0.662008000 0.436250000 2.637670000 H -1.644363000 1.918034000 2.554665000 H -1.863317000 0.781801000 3.900892000 74 (tBuPCP)Pd(CH3) complex (ωB97XD/BS1, CPCM: Benzene) G298K=-1789.301533 P 2.289993000 -0.146795000 0.087214000 C 0.005325000 1.622926000 -0.006067000 C -0.002771000 4.459369000 0.006410000 C 3.078608000 -0.180002000 -1.631716000 C -1.166623000 2.356996000 -0.296463000 C 1.174246000 2.360808000 0.287853000 C -1.170710000 3.756116000 -0.282509000 C 1.169380000 3.760292000 0.287051000 C 3.308920000 -1.102888000 1.359221000 C 0.024755000 -2.590620000 0.041418000 H -0.950719000 -3.063885000 -0.147378000 H 0.722826000 -3.008495000 -0.705260000 H 0.356530000 -2.959669000 1.029624000 C -3.080127000 -0.169387000 1.622294000 C -3.318867000 -1.108835000 -1.356668000 H -2.092310000 4.302359000 -0.506965000 H -0.006063000 5.552440000 0.011996000 H 2.088102000 4.309875000 0.515186000 C -2.421354000 1.602252000 -0.671007000 H -3.341966000 2.091997000 -0.314208000 H -2.500196000 1.561318000 -1.769863000 C 2.438542000 1.612422000 0.645569000 H 3.348636000 2.097144000 0.256113000 H 2.549352000 1.588460000 1.742136000 P -2.286364000 -0.151838000 -0.091634000 Pd 0.002273000 -0.464010000 0.003343000 C -2.389864000 -1.300455000 -2.568953000 H -1.508458000 -1.901751000 -2.303830000 H -2.938698000 -1.814555000 -3.374878000 H -2.031884000 -0.339606000 -2.971351000 C -4.579383000 -0.352821000 -1.805895000 H -4.343439000 0.603374000 -2.293453000 H -5.119794000 -0.967957000 -2.544194000 H -5.270448000 -0.152052000 -0.977083000 C -3.728148000 -2.489892000 -0.827661000 H -4.481662000 -2.423248000 -0.030469000 H -4.175224000 -3.070633000 -1.651033000 H -2.868859000 -3.058120000 -0.447539000 C -2.752940000 -1.507820000 2.303074000 H -3.125819000 -1.488420000 3.340277000 H -3.218936000 -2.364439000 1.799065000 H -1.667047000 -1.682206000 2.327438000 C -2.414005000 0.954967000 2.435096000 H -1.319466000 0.848319000 2.454656000 H -2.644882000 1.954170000 2.037990000 H -2.785662000 0.911118000 3.471690000 C -4.594708000 0.065720000 1.607535000 H -5.143771000 -0.761499000 1.136808000 H -4.958476000 0.149334000 2.644829000 H -4.864103000 0.999844000 1.091019000 C 2.455281000 0.975331000 -2.435109000 H 1.356813000 0.921904000 -2.439065000 H 2.741765000 1.962652000 -2.044804000 H 2.808817000 0.912437000 -3.477083000 C 4.601243000 -0.006836000 -1.620143000 H 5.115858000 -0.872902000 -1.180989000 H 4.913460000 0.897525000 -1.075727000 C 2.702117000 -1.496744000 -2.327997000 H 1.610433000 -1.599979000 -2.409371000 H 3.127910000 -1.503669000 -3.344785000 H 3.083956000 -2.380861000 -1.800379000 C 2.425119000 -1.174435000 2.618211000 H 1.479277000 -1.695193000 2.416498000 H 2.963524000 -1.719544000 3.410492000 H 2.182026000 -0.175348000 3.012184000 C 4.635427000 -0.423690000 1.731525000 H 5.127931000 -1.013691000 2.522114000 H 5.333341000 -0.361526000 0.887898000 H 4.488051000 0.590672000 2.129492000 C 3.578931000 -2.530120000 0.864896000 H 4.297740000 -2.549894000 0.033024000 H 4.015588000 -3.121524000 1.686339000 H 2.655195000 -3.030405000 0.542711000 H 4.961362000 0.094144000 -2.657162000 77 The TS1_Out for C-CO2 bond formation with (tBuPCP)Pd(CH3) complex (ωB97XD/BS1, CPCM: Benzene) G298K=-1977.646720 Img. Freq.=-688.1525 cm-1 P -2.278492000 -0.304975000 0.132940000 C 0.076405000 -1.960209000 -0.160500000 C 0.172924000 -4.765722000 -0.515953000 C -3.012533000 -0.085621000 -1.591972000 C 1.268591000 -2.605248000 -0.558939000 C -1.068620000 -2.761936000 0.044681000 C 1.312643000 -3.993458000 -0.724694000 C -1.016078000 -4.147894000 -0.137934000 C -3.350886000 0.479987000 1.474657000 C -0.028911000 2.307869000 0.451723000 H 0.976970000 2.496183000 0.808921000 H -0.234667000 2.197343000 -0.619037000 H -0.841061000 2.364032000 1.168949000 C 3.142917000 -0.299307000 1.645344000 C 3.264190000 1.047483000 -1.193120000 H 2.247455000 -4.473827000 -1.028672000 H 0.210704000 -5.849425000 -0.651247000 H -1.915235000 -4.750134000 0.022945000 C 2.494712000 -1.775961000 -0.854228000 H 3.433037000 -2.283088000 -0.578567000 H 2.549540000 -1.590844000 -1.939387000 C -2.356457000 -2.113718000 0.492317000 H -3.248473000 -2.588743000 0.053528000 H -2.456406000 -2.215748000 1.585262000 C -0.334054000 4.184909000 -0.188270000 O 0.735084000 4.646507000 -0.465251000 O -1.515301000 4.384573000 -0.159079000 P 2.323345000 -0.125275000 -0.044941000 Pd 0.015916000 0.071273000 0.119947000 C 2.315527000 1.324198000 -2.373771000 H 1.440191000 1.906303000 -2.054940000 H 2.848872000 1.912945000 -3.136915000 H 1.958641000 0.400449000 -2.855709000 C 4.560303000 0.418590000 -1.731174000 H 4.376236000 -0.498141000 -2.308818000 H 5.044720000 1.137377000 -2.411607000 H 5.279749000 0.184472000 -0.936634000 C 3.594853000 2.384107000 -0.515094000 H 4.302923000 2.269075000 0.317378000 H 4.072534000 3.043456000 -1.257634000 H 2.698434000 2.910990000 -0.159987000 C 2.751956000 0.907075000 2.513629000 H 3.200598000 0.793344000 3.513604000 H 3.102078000 1.862160000 2.099583000 H 1.660300000 0.969912000 2.634222000 C 2.563938000 -1.566421000 2.299291000 H 1.465095000 -1.540757000 2.339826000 H 2.859502000 -2.485012000 1.771875000 H 2.944727000 -1.636397000 3.330798000 C 4.668367000 -0.431973000 1.574310000 H 5.153237000 0.489251000 1.222971000 H 5.058896000 -0.641876000 2.583268000 H 4.982603000 -1.261983000 0.923111000 C -2.357775000 -1.131896000 -2.510787000 H -1.260137000 -1.070371000 -2.485355000 H -2.643810000 -2.160795000 -2.247730000 H -2.688832000 -0.946826000 -3.545287000 C -4.532779000 -0.278739000 -1.637645000 H -5.073251000 0.515780000 -1.105690000 H -4.839708000 -1.250602000 -1.221663000 C -2.633727000 1.311346000 -2.111681000 H -1.546336000 1.390651000 -2.259806000 H -3.113984000 1.476851000 -3.089415000 H -2.938232000 2.127635000 -1.443744000 C -2.492417000 0.469135000 2.753160000 H -1.583433000 1.076089000 2.645138000 H -3.081934000 0.879799000 3.588327000 H -2.182365000 -0.548567000 3.037485000 C -4.636995000 -0.316758000 1.749040000 H -5.189502000 0.176357000 2.565294000 H -5.305407000 -0.357551000 0.880537000 H -4.431629000 -1.346762000 2.074096000 C -3.716682000 1.928656000 1.120883000 H -4.446681000 1.977590000 0.300489000 H -4.186485000 2.400630000 1.998901000 H -2.853175000 2.546938000 0.836517000 H -4.865947000 -0.252576000 -2.687738000 77 The TS1_Inn for C-CO2 bond formation with (tBuPCP)Pd(CH3) complex (ωB97XD/BS1, CPCM: Benzene) G298K=-3493.237364 Img. Freq.=-543.4061 cm-1 P -2.270787000 0.217122000 0.133183000 P 2.345716000 -0.069291000 0.013740000 C -0.053998000 -2.466736000 0.841685000 H -0.966020000 -2.819917000 1.333184000 H 0.446607000 -1.768643000 1.545109000 H 0.659813000 -3.301964000 0.774938000 C -2.386759000 1.816794000 -0.775358000 H -2.945385000 1.631069000 -1.705708000 H -2.976818000 2.558926000 -0.215314000 C -3.696211000 -0.785199000 -0.604107000 C -2.591038000 0.668627000 1.945966000 C 2.604659000 1.151920000 -1.332175000 H 3.511531000 1.759084000 -1.184741000 H 2.753772000 0.570500000 -2.257087000 C 3.600454000 -1.440133000 -0.338464000 C 2.790880000 0.850174000 1.619421000 Pd -0.004436000 -0.366318000 -0.127732000 C -0.600758000 -3.030632000 -1.068877000 O -0.048123000 -2.442425000 -1.955513000 O -1.348648000 -3.921803000 -0.812591000 C 2.185622000 2.262897000 1.568348000 H 1.115450000 2.256696000 1.331051000 H 2.317080000 2.734913000 2.555307000 H 2.684898000 2.900480000 0.824928000 C 4.299056000 1.011723000 1.848606000 H 4.453375000 1.642310000 2.739172000 H 4.809199000 0.058256000 2.036531000 H 4.792734000 1.515751000 1.004423000 C 2.162529000 0.094574000 2.801016000 H 2.434008000 0.597542000 3.743137000 H 1.065331000 0.089489000 2.728855000 H 2.502330000 -0.948083000 2.870406000 C 4.985629000 -0.908537000 -0.739937000 H 5.497829000 -0.368757000 0.063692000 H 5.620965000 -1.766449000 -1.014249000 H 4.935252000 -0.252002000 -1.620940000 C 3.720800000 -2.377161000 0.871518000 H 4.325382000 -3.253688000 0.588204000 H 4.219248000 -1.902008000 1.727648000 H 2.738927000 -2.744684000 1.201946000 C 3.043441000 -2.243445000 -1.522726000 H 2.071428000 -2.692391000 -1.297965000 H 2.911052000 -1.624722000 -2.423201000 H 3.755478000 -3.045438000 -1.775377000 C -3.264757000 -1.129832000 -2.041701000 H -2.277831000 -1.602735000 -2.093463000 H -3.999438000 -1.823888000 -2.479259000 H -3.237064000 -0.236712000 -2.684579000 C -3.914163000 -2.071858000 0.201102000 H -4.652973000 -2.700682000 -0.321373000 H -2.995275000 -2.663984000 0.298703000 H -4.318523000 -1.860571000 1.201781000 C -5.023496000 -0.012401000 -0.689472000 H -5.728895000 -0.606895000 -1.292477000 H -5.490088000 0.147127000 0.288659000 H -4.920024000 0.963396000 -1.185764000 C -2.223892000 -0.517041000 2.850234000 H -2.418884000 -0.242813000 3.899643000 H -2.806537000 -1.420545000 2.627771000 H -1.160328000 -0.775119000 2.761881000 C -4.033877000 1.101173000 2.228190000 H -4.733612000 0.255904000 2.180136000 H -4.090054000 1.511920000 3.249332000 H -4.383142000 1.884686000 1.538948000 C -1.647211000 1.833179000 2.285034000 H -0.602693000 1.572794000 2.070305000 H -1.887932000 2.753426000 1.733278000 H -1.727037000 2.058557000 3.360451000 C -1.013311000 2.320787000 -1.132275000 C -0.896243000 3.608957000 -1.669865000 C 0.118787000 1.488135000 -0.986211000 C 0.333726000 4.091873000 -2.099473000 H -1.788978000 4.235117000 -1.758825000 C 1.358870000 1.994126000 -1.448723000 C 1.456658000 3.276292000 -1.995557000 H 0.418050000 5.098054000 -2.516980000 H 2.429698000 3.644165000 -2.332614000 42 (MePBP)Pd(CH3) complex (ωB97XD/BS1, CPCM: Benzene) G298K=-1453.195398 P 1.050028000 -2.239972000 0.000001000 P 1.036373000 2.247301000 -0.000010000 N -1.362849000 -1.149042000 -0.000058000 N -1.370265000 1.145649000 0.000000000 B -0.500924000 0.001149000 -0.000032000 C 3.704465000 -0.011248000 0.000060000 H 4.102115000 -0.544789000 -0.885410000 H 4.102136000 -0.545225000 0.885257000 H 4.178090000 0.987804000 0.000300000 C -0.825646000 -2.482666000 -0.000099000 H -1.131911000 -3.060737000 -0.890489000 H -1.132003000 -3.060826000 0.890201000 C 1.611398000 -3.228366000 -1.433519000 C 1.611238000 -3.228364000 1.433584000 C -2.682510000 -0.719134000 -0.000033000 C -3.877483000 -1.430153000 -0.000041000 H -3.875729000 -2.522828000 -0.000079000 C -5.080144000 -0.711736000 0.000002000 H -6.028015000 -1.255148000 -0.000002000 C -5.084616000 0.684676000 0.000053000 H -6.035955000 1.221996000 0.000090000 C -3.886595000 1.410778000 0.000058000 H -3.891808000 2.503440000 0.000099000 C -2.687098000 0.707412000 0.000011000 C -0.840401000 2.482242000 0.000146000 H -1.149544000 3.058615000 0.890635000 H -1.149688000 3.058879000 -0.890122000 C 1.593739000 3.238058000 -1.433490000 C 1.594010000 3.238281000 1.433207000 Pd 1.537512000 0.006628000 0.000029000 H 2.709683000 -3.194235000 -1.470953000 H 1.277110000 -4.274627000 -1.366935000 H 1.222206000 -2.776716000 -2.356990000 H 1.221948000 -2.776708000 2.357011000 H 1.276950000 -4.274622000 1.366966000 H 2.709520000 -3.194242000 1.471140000 H 1.255408000 4.282969000 -1.365902000 H 2.692086000 3.208252000 -1.471025000 H 1.205807000 2.785603000 -2.357067000 H 1.255640000 4.283174000 1.365546000 H 1.206288000 2.785946000 2.356932000 H 2.692365000 3.208506000 1.470515000 45 The TS1_Out for C-CO2 bond formation with (MePBP)Pd(CH3) complex (ωB97XD/BS1, CPCM: Benzene) G298K=-1641.549424 Img. Freq.=-678.7174 cm-1 P 0.009708000 2.488045000 0.000005000 P 0.876717000 -1.960134000 0.000006000 N -2.127439000 0.937014000 -0.000012000 N -1.686779000 -1.315894000 0.000013000 B -1.063653000 -0.024591000 0.000003000 C 3.163956000 0.693059000 -0.000001000 H 3.497240000 1.731101000 0.000002000 H 3.149503000 0.170781000 -0.960124000 H 3.149513000 0.170773000 0.960118000 C -1.869872000 2.351226000 -0.000032000 H -2.285566000 2.855095000 0.890614000 H -2.285526000 2.855062000 -0.890716000 C 0.378660000 3.554676000 1.437492000 C 0.378714000 3.554725000 -1.437432000 C -3.338868000 0.256463000 -0.000011000 C -4.648699000 0.722660000 -0.000024000 H -4.860019000 1.794606000 -0.000038000 C -5.687065000 -0.216488000 -0.000020000 H -6.722783000 0.131043000 -0.000029000 C -5.418850000 -1.587312000 -0.000002000 H -6.247317000 -2.299446000 0.000001000 C -4.103276000 -2.066243000 0.000010000 H -3.895217000 -3.138804000 0.000023000 C -3.065188000 -1.141222000 0.000005000 C -0.917394000 -2.531080000 0.000030000 H -1.114516000 -3.153467000 -0.890750000 H -1.114502000 -3.153432000 0.890837000 C 1.643580000 -2.792316000 1.431384000 C 1.643535000 -2.792303000 -1.431403000 Pd 0.914429000 0.363437000 0.000003000 C 4.929511000 -0.437412000 -0.000015000 O 5.852770000 0.309230000 -0.000015000 O 4.547030000 -1.574002000 -0.000020000 H 1.463067000 3.731374000 1.475606000 H -0.148386000 4.518238000 1.373011000 H 0.081162000 3.033774000 2.358492000 H 0.081260000 3.033851000 -2.358462000 H -0.148342000 4.518282000 -1.372943000 H 1.463121000 3.731432000 -1.475493000 H 2.718905000 -2.561647000 1.399584000 H 1.214757000 -2.398512000 2.363415000 H 1.498488000 -3.882017000 1.388211000 H 1.498448000 -3.882005000 -1.388233000 H 1.214679000 -2.398495000 -2.363417000 H 2.718860000 -2.561631000 -1.399639000 45 The TS1_Inn for C-CO2 bond formation with (MePBP)Pd(CH3) complex (ωB97XD/BS1, CPCM: Benzene) G298K=-1641.556780 Img. Freq.=-390.6978 cm-1 P 0.730253000 -2.194088000 0.084780000 P 0.535049000 2.322836000 0.069975000 N -1.690355000 -1.196511000 -0.025491000 N -1.788324000 1.096272000 -0.091901000 B -0.879694000 -0.012013000 -0.020383000 C 3.136333000 0.206155000 1.354775000 H 3.424747000 -0.766123000 1.778450000 H 2.543324000 0.763110000 2.109615000 H 4.052071000 0.809121000 1.245046000 C -1.116842000 -2.497839000 0.194189000 H -1.436200000 -3.240918000 -0.556843000 H -1.367958000 -2.899200000 1.192681000 C 1.170918000 -2.850021000 -1.561631000 C 1.493612000 -3.368229000 1.251800000 C -3.027006000 -0.818719000 -0.072249000 C -4.191641000 -1.578012000 -0.071255000 H -4.147137000 -2.668986000 -0.033282000 C -5.420218000 -0.908013000 -0.115657000 H -6.346031000 -1.487982000 -0.115242000 C -5.479408000 0.486877000 -0.158008000 H -6.450962000 0.985391000 -0.190572000 C -4.311919000 1.259583000 -0.157050000 H -4.359741000 2.350704000 -0.185918000 C -3.087403000 0.602562000 -0.114698000 C -1.337931000 2.455336000 0.047347000 H -1.688223000 2.911077000 0.990981000 H -1.670969000 3.104701000 -0.780944000 C 1.050027000 3.069328000 -1.512750000 C 1.069075000 3.533645000 1.328528000 Pd 1.110010000 0.078137000 0.306141000 C 3.554885000 -0.118761000 -0.759824000 O 3.468069000 0.908449000 -1.360700000 O 3.944545000 -1.245118000 -0.752162000 H 2.244343000 -2.682079000 -1.722694000 H 0.938965000 -3.922695000 -1.637152000 H 0.607680000 -2.295604000 -2.325475000 H 1.225650000 -3.092538000 2.281286000 H 1.183617000 -4.404383000 1.051002000 H 2.584174000 -3.282695000 1.139775000 H 0.735029000 4.120925000 -1.582402000 H 2.141582000 2.983772000 -1.594206000 H 0.604225000 2.492081000 -2.334948000 H 0.677555000 4.540184000 1.119392000 H 0.729319000 3.204675000 2.320791000 H 2.168352000 3.563678000 1.332305000 38 (MePCP)Pd(CH3) complex (ωB97XD/BS1, CPCM: Benzene) G298K=-1318.329759 P 2.263480000 -0.538953000 -0.029996000 C -0.018928000 1.177405000 -0.000350000 C -0.054950000 4.005251000 0.001121000 C -1.201874000 1.893335000 -0.298052000 C 1.145621000 1.922810000 0.298325000 C -1.218207000 3.292426000 -0.286584000 C 1.126038000 3.321926000 0.288179000 C 3.470088000 -1.557142000 0.888101000 C 0.081358000 -3.024914000 0.002725000 H -0.906392000 -3.515425000 -0.033703000 H 0.658710000 -3.402108000 -0.862186000 H 0.592352000 -3.391302000 0.912730000 C -2.977881000 -0.480090000 1.704814000 C -3.443186000 -1.638429000 -0.885422000 H -2.143000000 3.831952000 -0.513471000 H -0.068826000 5.098243000 0.001674000 H 2.036696000 3.884694000 0.515769000 C -2.443943000 1.104593000 -0.662342000 H -3.377414000 1.584621000 -0.325067000 H -2.517396000 0.993479000 -1.758723000 C 2.408403000 1.167199000 0.662927000 H 3.328705000 1.672739000 0.326822000 H 2.483891000 1.057226000 1.759278000 P -2.252629000 -0.597769000 0.029439000 Pd 0.009865000 -0.913224000 -0.001958000 C 2.989650000 -0.405700000 -1.703356000 H 4.039068000 -0.077207000 -1.659910000 H 2.930625000 -1.380812000 -2.207552000 H 2.401729000 0.320796000 -2.281908000 H 3.468268000 -2.573608000 0.468611000 H 4.486145000 -1.138988000 0.827854000 H 3.161273000 -1.621074000 1.941043000 H -4.464841000 -1.233990000 -0.825365000 H -3.134378000 -1.700301000 -1.938473000 H -3.428715000 -2.653774000 -0.463880000 H -4.034502000 -0.175264000 1.662921000 H -2.896220000 -1.452998000 2.210022000 H -2.405489000 0.260218000 2.281396000 41 The TS1_Out for C-CO2 bond formation with (MePCP)Pd(CH3) complex (ωB97XD/BS1, CPCM: Benzene) G298K=-1506.672359 Img. Freq.=-697.0757 cm-1 P -0.817167000 -1.960079000 0.116775000 C 1.644756000 -0.481654000 -0.049274000 C 4.259084000 -1.526434000 -0.281437000 C 2.730199000 0.347077000 -0.419438000 C 1.904863000 -1.850295000 0.195638000 C 4.023900000 -0.174728000 -0.521703000 C 3.201138000 -2.361548000 0.069903000 C -2.102056000 -2.611999000 1.231126000 C -2.350119000 1.084072000 0.141802000 H -2.401034000 2.159170000 0.310672000 H -2.522106000 0.428859000 0.997740000 C 1.383803000 2.842263000 1.747258000 C 0.279018000 3.762951000 -0.754511000 H 4.853714000 0.480326000 -0.802903000 H 5.270277000 -1.931024000 -0.370523000 H 3.386254000 -3.423390000 0.256935000 C 2.463062000 1.801711000 -0.739835000 H 3.293581000 2.467384000 -0.454604000 H 2.302152000 1.929915000 -1.824597000 C 0.767611000 -2.749105000 0.626414000 H 0.859336000 -3.775550000 0.236317000 H 0.740463000 -2.826097000 1.727546000 P 0.886072000 2.263740000 0.088194000 Pd -0.260271000 0.278969000 0.089836000 C -1.237722000 -2.661942000 -1.512471000 H -1.329056000 -3.757125000 -1.460335000 H -2.196331000 -2.227145000 -1.830650000 H -0.458503000 -2.390012000 -2.238003000 H -3.066787000 -2.197993000 0.902533000 H -2.134699000 -3.711390000 1.198352000 H -1.898297000 -2.281819000 2.259600000 H 1.039506000 4.558090000 -0.750989000 H 0.013046000 3.514203000 -1.791488000 H -0.625115000 4.123619000 -0.243577000 H 2.051748000 3.713931000 1.678841000 H 0.490049000 3.109856000 2.328485000 H 1.902334000 2.021449000 2.262467000 H -2.260711000 0.734436000 -0.892202000 C -4.223002000 0.510760000 -0.268670000 O -4.161038000 -0.668544000 -0.502225000 O -4.943731000 1.456802000 -0.184701000 41 The TS1_Inn for C-CO2 bond formation with (MePCP)Pd(CH3) complex (ωB97XD/BS1, CPCM: Benzene) G298K=-1506.679784 Img. Freq.=-428.8166 cm-1 P -1.165601000 -1.919364000 0.181480000 C 1.332305000 -0.645014000 -0.059875000 C 3.822047000 -1.893412000 -0.497379000 C 2.431046000 0.088966000 -0.561772000 C 1.510745000 -2.020091000 0.217358000 C 3.665253000 -0.535615000 -0.767713000 C 2.746629000 -2.633627000 -0.010999000 C -2.591668000 -2.491575000 1.154652000 C -2.306420000 1.330493000 1.074427000 H -2.178794000 2.418367000 1.147935000 H -3.374799000 1.091857000 1.159066000 C 1.701656000 2.574363000 1.785625000 C 0.295751000 3.733881000 -0.457855000 H 4.510146000 0.044390000 -1.150144000 H 4.787055000 -2.377162000 -0.667216000 H 2.870566000 -3.699765000 0.199941000 C 2.235514000 1.554940000 -0.876780000 H 3.156056000 2.149347000 -0.763285000 H 1.884120000 1.682891000 -1.915393000 C 0.337819000 -2.803332000 0.766613000 H 0.350224000 -3.863990000 0.469517000 H 0.330899000 -2.768106000 1.869790000 P 0.877244000 2.146381000 0.213453000 Pd -0.465829000 0.268146000 0.286667000 C -1.446383000 -2.562437000 -1.499577000 H -1.648268000 -3.643689000 -1.475223000 H -2.297360000 -2.023992000 -1.936384000 H -0.549608000 -2.367674000 -2.104231000 H -3.474847000 -1.957863000 0.775417000 H -2.740998000 -3.577062000 1.058102000 H -2.445394000 -2.229848000 2.211930000 H 1.134113000 4.426962000 -0.621850000 H -0.244424000 3.542093000 -1.394067000 H -0.414527000 4.181214000 0.252126000 H 2.436985000 3.380266000 1.641895000 H 0.947530000 2.895034000 2.518639000 H 2.208238000 1.679387000 2.173941000 H -1.860974000 0.859798000 1.978652000 C -2.623556000 1.015271000 -0.931116000 O -3.292966000 0.023291000 -1.058345000 O -2.244145000 1.994300000 -1.510841000 78 (tBuPBP)Ni(CH3) complex (ωB97XD/BS1, CPCM: Benzene) G298K=-3304.392597 P -2.143613000 -0.579005000 -0.064854000 P 2.149641000 -0.550777000 0.059487000 N -1.136178000 1.810539000 -0.259047000 N 1.094731000 1.828659000 0.193088000 B -0.013323000 0.940306000 -0.031475000 C 0.010880000 -3.001676000 -0.141151000 H -0.364235000 -3.350952000 -1.125078000 H -0.641695000 -3.494009000 0.605417000 H 0.989548000 -3.500294000 -0.035621000 C -2.424291000 1.234424000 -0.512067000 H -2.718777000 1.328693000 -1.570982000 H -3.228412000 1.690779000 0.091016000 C -3.226611000 -1.466395000 -1.335438000 C -4.573120000 -0.785681000 -1.622402000 H -4.456596000 0.240746000 -1.998273000 H -5.230253000 -0.755585000 -0.744728000 H -5.099136000 -1.356339000 -2.405767000 C -3.473406000 -2.919604000 -0.910164000 H -3.927259000 -3.471184000 -1.749987000 H -4.172423000 -2.984681000 -0.063375000 H -2.540019000 -3.428533000 -0.635171000 C -2.381993000 -1.456372000 -2.623633000 H -2.941756000 -1.947757000 -3.436269000 H -1.432601000 -1.990585000 -2.480580000 H -2.145675000 -0.432513000 -2.955231000 C -2.862514000 -0.684553000 1.687124000 C -2.183665000 0.414531000 2.526004000 H -2.533976000 0.330941000 3.567748000 H -2.423479000 1.429235000 2.176799000 H -1.089057000 0.306794000 2.526802000 C -4.381290000 -0.492730000 1.749436000 H -4.698266000 -0.448695000 2.804440000 H -4.922224000 -1.328037000 1.283223000 H -4.707804000 0.443060000 1.270854000 C -2.485751000 -2.040099000 2.303630000 H -1.395395000 -2.171535000 2.333293000 H -2.908105000 -2.889393000 1.750384000 H -2.870021000 -2.086924000 3.335933000 C -0.731562000 3.130946000 -0.171658000 C -1.434875000 4.322517000 -0.311100000 H -2.503775000 4.315364000 -0.537943000 C -0.739097000 5.528551000 -0.154121000 H -1.276430000 6.474118000 -0.259355000 C 0.627599000 5.539613000 0.133265000 H 1.146785000 6.493744000 0.251522000 C 1.346236000 4.345069000 0.274135000 H 2.414956000 4.355304000 0.501677000 C 0.665658000 3.142276000 0.119116000 C 2.382710000 1.275265000 0.491310000 H 2.637153000 1.388464000 1.558054000 H 3.199207000 1.738469000 -0.089210000 C 2.953918000 -0.677987000 -1.649385000 C 2.259892000 0.363642000 -2.547104000 H 2.664127000 0.277665000 -3.568938000 H 2.426627000 1.397065000 -2.210116000 H 1.173615000 0.195951000 -2.596577000 C 4.463158000 -0.412921000 -1.648694000 H 5.021169000 -1.191493000 -1.109989000 H 4.718255000 0.563092000 -1.208347000 H 4.831924000 -0.408292000 -2.687677000 C 2.666943000 -2.068316000 -2.237287000 H 3.063315000 -2.114009000 -3.265083000 H 1.587343000 -2.270019000 -2.271206000 H 3.138051000 -2.876213000 -1.662704000 C 3.188889000 -1.402373000 1.396317000 C 2.239061000 -1.493791000 2.604217000 H 2.769855000 -1.934446000 3.464173000 H 1.366833000 -2.122448000 2.370622000 H 1.868225000 -0.502668000 2.912633000 C 3.602230000 -2.820898000 0.983566000 H 4.363613000 -2.815447000 0.190465000 H 2.746604000 -3.417973000 0.644056000 H 4.043399000 -3.332252000 1.854859000 C 4.451612000 -0.625274000 1.801113000 H 5.000686000 -1.209396000 2.558048000 H 4.223590000 0.348800000 2.254945000 H 5.134334000 -0.458300000 0.957764000 Ni 0.007172000 -0.998088000 -0.040253000 81 The TS1_Out for C-CO2 bond formation with (tBuPBP)Ni(CH3) complex (ωB97XD/BS1, CPCM: Benzene) G298K=-3492.741167 Img. Freq.=-645.6621 cm-1 P 1.133700000 1.827509000 -0.193106000 P -0.829154000 -2.033814000 -0.051956000 N -1.454573000 1.975969000 -0.255462000 N -2.429720000 -0.012028000 0.277942000 B -1.173127000 0.579808000 -0.079218000 C 2.359834000 -1.274984000 -0.442582000 H 2.923289000 -0.666118000 -1.144054000 H 2.145595000 -2.298209000 -0.731461000 H 2.284408000 -0.968991000 0.609935000 C -0.381941000 2.878690000 -0.556431000 H -0.403298000 3.793590000 0.060186000 H -0.387305000 3.195369000 -1.612703000 C 1.594170000 2.331519000 1.573865000 C 2.388603000 2.449515000 -1.461512000 C -2.795555000 2.213839000 -0.000600000 C -3.542547000 3.386612000 -0.022703000 H -3.077620000 4.339992000 -0.284892000 C -4.903508000 3.312081000 0.298283000 H -5.506378000 4.223151000 0.287575000 C -5.500711000 2.093398000 0.629981000 H -6.564662000 2.063296000 0.876380000 C -4.757424000 0.906907000 0.653947000 H -5.224971000 -0.044764000 0.917642000 C -3.404799000 0.970692000 0.337530000 C -2.492537000 -1.412957000 0.574730000 H -3.336461000 -1.924679000 0.081253000 H -2.586195000 -1.596612000 1.657809000 C -0.390319000 -3.374759000 1.211549000 C -1.249383000 -2.750251000 -1.752271000 C 4.095505000 -1.841853000 0.540344000 O 4.853587000 -0.921114000 0.463703000 O 3.906644000 -2.944243000 0.958782000 C -1.979996000 -1.647132000 -2.540548000 H -1.370000000 -0.735521000 -2.626004000 H -2.180675000 -2.015820000 -3.559386000 H -2.945065000 -1.368828000 -2.093229000 C -2.140223000 -3.995726000 -1.691094000 H -2.426040000 -4.285897000 -2.715220000 H -1.622629000 -4.855033000 -1.242732000 H -3.070887000 -3.819168000 -1.130774000 C 0.052710000 -3.076263000 -2.500592000 H -0.196528000 -3.469709000 -3.499439000 H 0.672897000 -2.178267000 -2.632236000 H 0.660377000 -3.833737000 -1.987789000 C -1.612208000 -4.178191000 1.686926000 H -2.109795000 -4.717004000 0.870889000 H -1.275244000 -4.930402000 2.418410000 H -2.361214000 -3.554193000 2.193558000 C 0.668022000 -4.352088000 0.682698000 H 0.937552000 -5.046861000 1.494482000 H 0.293757000 -4.960916000 -0.152473000 H 1.597011000 -3.849929000 0.382387000 C 0.204635000 -2.608896000 2.407966000 H 1.174155000 -2.159894000 2.149946000 H -0.463452000 -1.811472000 2.771890000 H 0.374654000 -3.307854000 3.242510000 C 0.327725000 2.224603000 2.443711000 H -0.117373000 1.219573000 2.404188000 H 0.604425000 2.429396000 3.490471000 H -0.447920000 2.950573000 2.159694000 C 2.629643000 1.335381000 2.122220000 H 2.979727000 1.683400000 3.107283000 H 2.180321000 0.342231000 2.271465000 H 3.509057000 1.208113000 1.477530000 C 2.138041000 3.761010000 1.676642000 H 2.275907000 4.017566000 2.739487000 H 3.114784000 3.872487000 1.186915000 H 1.446478000 4.503116000 1.249519000 C 3.822517000 2.072265000 -1.063301000 H 4.492329000 2.268796000 -1.916154000 H 4.184637000 2.680921000 -0.222351000 H 3.943502000 1.016843000 -0.783491000 C 2.320704000 3.965797000 -1.704643000 H 2.552958000 4.551386000 -0.806811000 H 3.066273000 4.232884000 -2.471321000 H 1.341455000 4.290388000 -2.084004000 C 2.008531000 1.726821000 -2.767811000 H 2.114710000 0.636932000 -2.677147000 H 0.969443000 1.936511000 -3.068954000 H 2.666048000 2.070904000 -3.582348000 Ni 0.529167000 -0.301890000 -0.234267000 81 The TS1_Inn for C-CO2 bond formation with (tBuPBP)Ni(CH3) complex (ωB97XD/BS1, CPCM: Benzene) G298K=-3492.735926 Img. Freq.=-395.8286 cm-1 P -2.127893000 -0.703371000 0.038096000 P 2.207368000 0.010591000 -0.172752000 N -1.383748000 1.671014000 0.710743000 N 0.704810000 2.114801000 -0.064057000 B -0.163563000 1.030777000 0.298969000 C 0.231236000 -2.691328000 -1.058359000 H -0.453674000 -3.547718000 -0.962387000 H -0.231210000 -2.049315000 -1.833612000 H 1.171790000 -3.070506000 -1.474012000 C -2.543989000 0.867884000 0.971192000 H -3.471514000 1.338001000 0.614573000 H -2.670911000 0.658066000 2.043689000 C -2.767236000 -0.310870000 -1.727328000 C -3.241256000 -1.983454000 0.888542000 C -1.261843000 3.044408000 0.579181000 C -2.162300000 4.076587000 0.820295000 H -3.166805000 3.866374000 1.195395000 C -1.745890000 5.390691000 0.573100000 H -2.439596000 6.214688000 0.756058000 C -0.459888000 5.663450000 0.100395000 H -0.160208000 6.698001000 -0.082701000 C 0.453330000 4.630631000 -0.145935000 H 1.456725000 4.844020000 -0.522072000 C 0.046960000 3.322608000 0.093698000 C 2.009418000 1.831845000 -0.578473000 H 2.800489000 2.443889000 -0.112852000 H 2.069512000 1.991610000 -1.668674000 C 3.341100000 -0.568953000 -1.574571000 C 3.135497000 0.094403000 1.489479000 C 0.863205000 -3.118345000 0.996867000 O 0.136640000 -2.657929000 1.824157000 O 1.762869000 -3.840605000 0.733581000 C 2.326638000 1.004298000 2.432445000 H 1.291894000 0.651677000 2.551675000 H 2.804786000 0.987347000 3.425040000 H 2.295235000 2.050833000 2.097501000 C 4.557030000 0.656127000 1.365888000 H 4.960958000 0.820045000 2.378012000 H 5.233669000 -0.045339000 0.859016000 H 4.594566000 1.621973000 0.840777000 C 3.204002000 -1.295487000 2.137165000 H 3.828769000 -1.233283000 3.042937000 H 2.207970000 -1.632673000 2.449418000 H 3.639045000 -2.060349000 1.482319000 C 4.474933000 0.410068000 -1.920346000 H 5.203694000 0.530670000 -1.111913000 H 5.020435000 0.015243000 -2.793135000 H 4.102462000 1.406129000 -2.200493000 C 3.934030000 -1.942716000 -1.235364000 H 4.394255000 -2.374883000 -2.138854000 H 4.723993000 -1.863765000 -0.473818000 H 3.176530000 -2.648312000 -0.866326000 C 2.437264000 -0.687026000 -2.816225000 H 1.659148000 -1.447128000 -2.690199000 H 1.947215000 0.267555000 -3.065336000 H 3.054524000 -0.972974000 -3.683145000 C -1.664595000 0.460672000 -2.478328000 H -0.739789000 -0.123061000 -2.584089000 H -2.028804000 0.700565000 -3.490835000 H -1.409528000 1.407336000 -1.981644000 C -3.041092000 -1.616848000 -2.489529000 H -3.239161000 -1.376188000 -3.546534000 H -2.183463000 -2.303796000 -2.463644000 H -3.923326000 -2.147838000 -2.106847000 C -4.029427000 0.564467000 -1.752287000 H -4.383024000 0.643368000 -2.793129000 H -4.855370000 0.157892000 -1.155715000 H -3.822239000 1.588795000 -1.409864000 C -2.898234000 -3.401378000 0.410582000 H -3.576284000 -4.116460000 0.904332000 H -3.010990000 -3.533049000 -0.672685000 H -1.871069000 -3.663917000 0.688987000 C -4.737256000 -1.709331000 0.688241000 H -5.063464000 -1.871745000 -0.348208000 H -5.313071000 -2.403144000 1.322682000 H -5.018546000 -0.687542000 0.986206000 C -2.932329000 -1.915688000 2.397953000 H -1.852288000 -1.924358000 2.594300000 H -3.383783000 -1.036553000 2.878881000 H -3.366886000 -2.804176000 2.883502000 Ni 0.142988000 -0.853604000 -0.044141000 3 Carbon dioxide (PBE0-D3BJ/BS1, CPCM: Benzene) G298K=-188.254432 C 0.000000000 0.000000000 0.000000000 O 0.000000000 0.000000000 1.159253000 O 0.000000000 0.000000000 -1.159253000 78 (tBuPBP)Pd(CH3) complex (PBE0-D3BJ/BS1, CPCM: Benzene) G298K=-1922.945242 P -2.250276000 -0.492450000 -0.051051000 P 2.253868000 -0.490931000 0.051104000 N -1.133265000 1.887378000 -0.207998000 N 1.123388000 1.892811000 0.154473000 B -0.003250000 1.016817000 -0.020150000 C -0.034232000 -3.174164000 -0.192120000 H -0.412949000 -3.476518000 -1.188068000 H -0.710466000 -3.637487000 0.549268000 H 0.941456000 -3.675507000 -0.079009000 C -2.437344000 1.344317000 -0.440160000 H -2.756875000 1.468390000 -1.489512000 H -3.214783000 1.808594000 0.191984000 C -3.333992000 -1.303903000 -1.362388000 C -4.664855000 -0.595560000 -1.620996000 H -4.531655000 0.450176000 -1.934219000 H -5.329420000 -0.609830000 -0.748091000 H -5.189100000 -1.113010000 -2.441954000 C -3.582118000 -2.764654000 -0.985417000 H -4.030841000 -3.288890000 -1.845472000 H -4.283760000 -2.858395000 -0.143872000 H -2.645684000 -3.277619000 -0.723856000 C -2.476802000 -1.256373000 -2.634192000 H -3.022810000 -1.737620000 -3.462424000 H -1.523124000 -1.783588000 -2.483762000 H -2.247921000 -0.223841000 -2.941843000 C -2.970314000 -0.629371000 1.691589000 C -2.228655000 0.405463000 2.547585000 H -2.555787000 0.298077000 3.594820000 H -2.433966000 1.440996000 2.239864000 H -1.140124000 0.248573000 2.507741000 C -4.472913000 -0.367965000 1.763689000 H -4.786762000 -0.351148000 2.820764000 H -5.053761000 -1.156346000 1.264798000 H -4.753936000 0.601486000 1.324394000 C -2.646365000 -2.018311000 2.247550000 H -1.565002000 -2.213599000 2.205094000 H -3.152035000 -2.822433000 1.697349000 H -2.974579000 -2.071735000 3.298770000 C -0.712531000 3.203760000 -0.148590000 C -1.410803000 4.400225000 -0.272727000 H -2.487960000 4.399897000 -0.457676000 C -0.700568000 5.601854000 -0.155170000 H -1.234902000 6.550651000 -0.249114000 C 0.676175000 5.605226000 0.079111000 H 1.206755000 6.556630000 0.167809000 C 1.391124000 4.407054000 0.203210000 H 2.468311000 4.411985000 0.387917000 C 0.697432000 3.207212000 0.086381000 C 2.427309000 1.357575000 0.402743000 H 2.740338000 1.507982000 1.450133000 H 3.206024000 1.811607000 -0.234865000 C 3.085806000 -0.681280000 -1.632705000 C 2.361581000 0.298870000 -2.564952000 H 2.749419000 0.169733000 -3.588694000 H 2.514145000 1.350497000 -2.281462000 H 1.277995000 0.104859000 -2.578781000 C 4.582339000 -0.379269000 -1.626874000 H 5.151575000 -1.129597000 -1.060062000 H 4.811454000 0.614952000 -1.213518000 H 4.960348000 -0.397621000 -2.662750000 C 2.831829000 -2.099787000 -2.149332000 H 3.188913000 -2.173331000 -3.189835000 H 1.758966000 -2.340143000 -2.124977000 H 3.358786000 -2.862489000 -1.561558000 C 3.241307000 -1.264362000 1.460410000 C 2.285881000 -1.198388000 2.659092000 H 2.772421000 -1.642349000 3.543381000 H 1.357918000 -1.752042000 2.447922000 H 2.009997000 -0.162768000 2.913495000 C 3.538217000 -2.729769000 1.144453000 H 4.304455000 -2.835986000 0.363022000 H 2.631903000 -3.262565000 0.824485000 H 3.923852000 -3.223882000 2.051543000 C 4.543646000 -0.537930000 1.801997000 H 5.021863000 -1.049215000 2.654255000 H 4.379685000 0.505821000 2.105841000 H 5.261301000 -0.544401000 0.971709000 Pd 0.002715000 -1.008793000 -0.048467000 81 The TS1_Out for C-CO2 bond formation with (tBuPBP)Pd(CH3) complex (PBE0-D3BJ/BS1, CPCM: Benzene) G298K=-2111.169281 Img. Freq.=-597.6131 cm-1 P -1.263911000 1.943275000 -0.007698000 P 1.391235000 -1.745804000 0.109669000 N -2.508195000 -0.368607000 -0.221326000 N -1.200504000 -2.202718000 0.176476000 B -1.154130000 -0.778025000 0.016607000 C 2.309609000 1.738212000 0.272667000 H 1.934915000 2.710996000 0.572316000 H 2.402962000 1.504822000 -0.792067000 H 2.814598000 1.132344000 1.021089000 C -2.831027000 1.004392000 -0.465357000 H -3.690658000 1.355436000 0.131512000 H -3.076543000 1.187301000 -1.525366000 C -1.668222000 2.664628000 1.688416000 C -1.136193000 3.237126000 -1.373973000 C -3.326019000 -1.486573000 -0.214763000 C -4.696913000 -1.622551000 -0.404943000 H -5.321921000 -0.749034000 -0.606463000 C -5.253324000 -2.905252000 -0.332776000 H -6.329020000 -3.030689000 -0.479197000 C -4.456466000 -4.023839000 -0.077634000 H -4.916472000 -5.013776000 -0.025427000 C -3.075155000 -3.899315000 0.113595000 H -2.454181000 -4.775666000 0.315161000 C -2.510958000 -2.630184000 0.041698000 C -0.011701000 -2.951819000 0.450621000 H 0.080940000 -3.854481000 -0.178113000 H 0.034569000 -3.281477000 1.502601000 C 2.658404000 -2.175436000 1.438141000 C 1.961017000 -2.209664000 -1.628647000 Pd 0.466176000 0.396581000 0.119765000 C 4.203954000 2.435585000 -0.234612000 O 4.113811000 3.617830000 -0.361347000 O 4.908659000 1.470215000 -0.287778000 C 0.709659000 -2.231478000 -2.515236000 H 0.165472000 -1.276140000 -2.466255000 H 1.021155000 -2.395330000 -3.559690000 H 0.010121000 -3.036773000 -2.247945000 C 2.654261000 -3.569025000 -1.698557000 H 2.856958000 -3.814658000 -2.754006000 H 3.618931000 -3.571515000 -1.172892000 H 2.031327000 -4.379180000 -1.289370000 C 2.890549000 -1.107560000 -2.146195000 H 3.249541000 -1.382728000 -3.151295000 H 2.350819000 -0.153338000 -2.232510000 H 3.766535000 -0.933700000 -1.508452000 C 2.786883000 -3.678010000 1.703658000 H 3.144807000 -4.234130000 0.828327000 H 3.521215000 -3.830150000 2.511922000 H 1.843052000 -4.131435000 2.038831000 C 4.029408000 -1.603002000 1.075446000 H 4.693001000 -1.689240000 1.951479000 H 4.502183000 -2.163385000 0.256134000 H 4.002075000 -0.543596000 0.783135000 C 2.132561000 -1.485292000 2.703609000 H 2.063503000 -0.395934000 2.568677000 H 1.133828000 -1.850936000 2.990611000 H 2.816637000 -1.690993000 3.543009000 C -2.119926000 1.481442000 2.554462000 H -1.356093000 0.689201000 2.578960000 H -2.277715000 1.837742000 3.585321000 H -3.063667000 1.034203000 2.210350000 C -0.387722000 3.236323000 2.302121000 H -0.605879000 3.590153000 3.322890000 H 0.396778000 2.468158000 2.361907000 H 0.013983000 4.085844000 1.734077000 C -2.761968000 3.729533000 1.658453000 H -3.023983000 4.006625000 2.692922000 H -2.431007000 4.646235000 1.150494000 H -3.683445000 3.374876000 1.171943000 C -0.114731000 4.311642000 -1.000518000 H 0.045492000 4.968496000 -1.870993000 H -0.465056000 4.946828000 -0.174281000 H 0.859325000 3.882635000 -0.727483000 C -2.470435000 3.898474000 -1.727454000 H -2.882907000 4.486866000 -0.898564000 H -2.308754000 4.588746000 -2.571835000 H -3.232276000 3.173302000 -2.047467000 C -0.617115000 2.456676000 -2.588913000 H 0.367618000 2.011002000 -2.383855000 H -1.298779000 1.645183000 -2.888030000 H -0.516758000 3.141315000 -3.446796000 81 The TS1_Inn for C-CO2 bond formation with (tBuPBP)Pd(CH3) complex (PBE0-D3BJ/BS1, CPCM: Benzene) G298K=-2111.161857 Img. Freq.=-432.7823 cm-1 P -2.265542000 0.089642000 0.229569000 P 2.244050000 -0.614015000 0.087630000 N -0.751233000 2.190105000 -0.296320000 N 1.463445000 1.763263000 -0.660191000 B 0.208767000 1.125579000 -0.361772000 C -0.379257000 -3.092145000 0.323690000 H -1.360711000 -3.471692000 0.629024000 H 0.139485000 -2.722629000 1.231831000 H 0.233551000 -3.949473000 0.002351000 C -2.141588000 1.940097000 -0.081661000 H -2.742621000 2.206265000 -0.966649000 H -2.552194000 2.511231000 0.769167000 C -3.674319000 -0.393357000 -0.933062000 C -2.762803000 -0.012552000 2.051935000 C -0.114384000 3.396027000 -0.538101000 C -0.602595000 4.697180000 -0.582937000 H -1.663630000 4.902021000 -0.420259000 C 0.301137000 5.735704000 -0.838407000 H -0.063474000 6.765238000 -0.875913000 C 1.657780000 5.475968000 -1.046436000 H 2.341932000 6.304857000 -1.244474000 C 2.157796000 4.168606000 -1.011468000 H 3.218021000 3.967371000 -1.183596000 C 1.268337000 3.129878000 -0.758111000 C 2.685449000 1.020026000 -0.708114000 H 3.504959000 1.518930000 -0.162288000 H 3.035028000 0.847094000 -1.740522000 C 3.426671000 -1.823649000 -0.749724000 C 2.707459000 -0.327194000 1.909829000 Pd -0.116179000 -0.829605000 -0.080067000 C -0.915560000 -3.061279000 -1.789327000 O -0.268077000 -2.312537000 -2.455871000 O -1.736245000 -3.914766000 -1.743919000 C 2.162894000 1.043193000 2.328475000 H 1.094118000 1.152029000 2.102483000 H 2.294175000 1.153898000 3.417146000 H 2.696133000 1.874901000 1.846393000 C 4.210830000 -0.344761000 2.179727000 H 4.383222000 -0.064297000 3.231950000 H 4.652320000 -1.339425000 2.032634000 H 4.757285000 0.378270000 1.556083000 C 2.018347000 -1.400546000 2.755746000 H 2.276607000 -1.249711000 3.816645000 H 0.924926000 -1.336248000 2.659685000 H 2.321423000 -2.419660000 2.478346000 C 4.868919000 -1.322251000 -0.861757000 H 5.383023000 -1.253974000 0.102940000 H 5.434570000 -2.034950000 -1.484731000 H 4.933770000 -0.343091000 -1.359219000 C 3.379633000 -3.161539000 -0.011315000 H 3.937526000 -3.915224000 -0.590693000 H 3.842090000 -3.106485000 0.984882000 H 2.347080000 -3.521371000 0.102044000 C 2.871398000 -2.012249000 -2.164737000 H 1.830423000 -2.356536000 -2.159266000 H 2.909350000 -1.080924000 -2.750861000 H 3.490209000 -2.755955000 -2.693202000 C -3.062918000 -0.298799000 -2.337033000 H -2.163946000 -0.918690000 -2.446570000 H -3.807578000 -0.634099000 -3.076956000 H -2.786487000 0.735538000 -2.595244000 C -4.110704000 -1.829526000 -0.644760000 H -4.773441000 -2.173461000 -1.455526000 H -3.262965000 -2.525377000 -0.597283000 H -4.681307000 -1.897786000 0.292814000 C -4.897581000 0.526332000 -0.876068000 H -5.593543000 0.221027000 -1.674868000 H -5.442084000 0.456076000 0.072456000 H -4.651424000 1.582902000 -1.055302000 C -2.721358000 -1.472635000 2.507242000 H -2.937802000 -1.516845000 3.587253000 H -3.462089000 -2.098312000 1.993009000 H -1.731231000 -1.916597000 2.337703000 C -4.134264000 0.588027000 2.353165000 H -4.949774000 -0.030503000 1.955048000 H -4.269224000 0.639120000 3.446218000 H -4.248252000 1.609867000 1.960815000 C -1.686850000 0.753186000 2.827836000 H -0.692071000 0.326569000 2.640203000 H -1.652561000 1.823748000 2.577702000 H -1.895772000 0.670276000 3.906662000 74 (tBuPCP)Pd(CH3) complex (PBE0-D3BJ/BS1, CPCM: Benzene) G298K=-1788.178349 P 2.276779000 -0.151864000 0.084632000 C 0.006557000 1.617949000 -0.003206000 C -0.000616000 4.453299000 0.010734000 C 3.049804000 -0.180993000 -1.638901000 C -1.166011000 2.351658000 -0.294546000 C 1.176780000 2.354392000 0.291617000 C -1.169088000 3.751032000 -0.279262000 C 1.171719000 3.754134000 0.291231000 C 3.303885000 -1.104953000 1.349598000 C 0.018068000 -2.575265000 0.069878000 H -0.965915000 -3.044159000 -0.076333000 H 0.687450000 -2.998262000 -0.698743000 H 0.385649000 -2.931269000 1.049200000 C -3.069234000 -0.173267000 1.621364000 C -3.295869000 -1.110097000 -1.360605000 H -2.090568000 4.297911000 -0.503936000 H -0.003593000 5.546744000 0.017108000 H 2.090758000 4.303539000 0.519781000 C -2.414353000 1.596983000 -0.667584000 H -3.337482000 2.083324000 -0.311581000 H -2.496588000 1.549160000 -1.766800000 C 2.435065000 1.604757000 0.644052000 H 3.346745000 2.086239000 0.253246000 H 2.552152000 1.571460000 1.740639000 P -2.272697000 -0.155425000 -0.088312000 Pd 0.001239000 -0.458670000 0.013341000 C -2.357144000 -1.283123000 -2.561222000 H -1.461586000 -1.858046000 -2.284386000 H -2.886898000 -1.814640000 -3.369166000 H -2.020980000 -0.314671000 -2.964171000 C -4.553941000 -0.359786000 -1.807186000 H -4.322386000 0.607778000 -2.273947000 H -5.079640000 -0.966706000 -2.563346000 H -5.256213000 -0.182451000 -0.982254000 C -3.695935000 -2.491080000 -0.839870000 H -4.443133000 -2.432041000 -0.036177000 H -4.147743000 -3.066807000 -1.664709000 H -2.831734000 -3.059202000 -0.470712000 C -2.743589000 -1.508755000 2.296118000 H -3.101797000 -1.485523000 3.338710000 H -3.221516000 -2.362732000 1.798657000 H -1.658024000 -1.687465000 2.303310000 C -2.393385000 0.945089000 2.423410000 H -1.299046000 0.831258000 2.427750000 H -2.622165000 1.944879000 2.027081000 H -2.754605000 0.902804000 3.464174000 C -4.577295000 0.067598000 1.602141000 H -5.128533000 -0.755566000 1.126562000 H -4.943714000 0.149625000 2.639143000 H -4.840922000 1.004853000 1.088415000 C 2.406139000 0.967875000 -2.424156000 H 1.308265000 0.900384000 -2.408375000 H 2.685486000 1.956016000 -2.031294000 H 2.745521000 0.913406000 -3.471705000 C 4.565932000 0.002023000 -1.639142000 H 5.090321000 -0.856614000 -1.196867000 H 4.875983000 0.912849000 -1.104492000 C 2.671486000 -1.495321000 -2.326460000 H 1.578862000 -1.612574000 -2.368030000 H 3.061570000 -1.489885000 -3.357808000 H 3.085315000 -2.375767000 -1.817109000 C 2.426483000 -1.160834000 2.607057000 H 1.465116000 -1.651851000 2.402475000 H 2.952937000 -1.725474000 3.394232000 H 2.212709000 -0.157359000 3.006888000 C 4.630608000 -0.429530000 1.704269000 H 5.123429000 -1.010883000 2.501649000 H 5.324396000 -0.383508000 0.855948000 H 4.489712000 0.591235000 2.088052000 C 3.559872000 -2.530028000 0.857442000 H 4.263937000 -2.554828000 0.013246000 H 4.008545000 -3.119731000 1.674142000 H 2.628964000 -3.027788000 0.552669000 H 4.917101000 0.097960000 -2.680218000 77 The TS1_Out for C-CO2 bond formation with (tBuPCP)Pd(CH3) complex (PBE0-D3BJ/BS1, CPCM: Benzene) G298K=-1976.393694 Img. Freq.=-616.5772 cm-1 P -2.266315000 -0.298290000 0.125391000 C 0.078959000 -1.958652000 -0.147632000 C 0.178619000 -4.766796000 -0.462502000 C -3.001190000 -0.103646000 -1.599585000 C 1.273482000 -2.606207000 -0.535633000 C -1.066233000 -2.757009000 0.070714000 C 1.318449000 -3.996959000 -0.681456000 C -1.011673000 -4.145601000 -0.092923000 C -3.337238000 0.497044000 1.460823000 C -0.030859000 2.298387000 0.412943000 H 0.974862000 2.476282000 0.774372000 H -0.231496000 2.189730000 -0.658870000 H -0.847175000 2.332915000 1.126816000 C 3.119384000 -0.275379000 1.649210000 C 3.257413000 1.034348000 -1.207277000 H 2.254322000 -4.480917000 -0.977459000 H 0.217567000 -5.852680000 -0.582530000 H -1.910263000 -4.746778000 0.076884000 C 2.493604000 -1.778788000 -0.834068000 H 3.433315000 -2.278347000 -0.548010000 H 2.556923000 -1.599741000 -1.920683000 C -2.347105000 -2.101366000 0.509432000 H -3.242519000 -2.581304000 0.082142000 H -2.447322000 -2.179769000 1.605214000 C -0.335895000 4.183746000 -0.164879000 O 0.734504000 4.661272000 -0.412850000 O -1.519115000 4.379199000 -0.144683000 P 2.311266000 -0.119297000 -0.046561000 Pd 0.016266000 0.068151000 0.104387000 C 2.318636000 1.271444000 -2.397185000 H 1.421978000 1.829169000 -2.094668000 H 2.845114000 1.866827000 -3.160637000 H 1.994157000 0.332619000 -2.872730000 C 4.557842000 0.402222000 -1.714641000 H 4.386225000 -0.537211000 -2.258786000 H 5.036065000 1.102025000 -2.419541000 H 5.276593000 0.206235000 -0.909177000 C 3.569196000 2.381579000 -0.553439000 H 4.257910000 2.285351000 0.297512000 H 4.064706000 3.024238000 -1.299622000 H 2.665282000 2.916504000 -0.230159000 C 2.722812000 0.936246000 2.497634000 H 3.150830000 0.825313000 3.507303000 H 3.088871000 1.885616000 2.084047000 H 1.629262000 1.006121000 2.595030000 C 2.527320000 -1.530322000 2.301399000 H 1.427866000 -1.496826000 2.321160000 H 2.825102000 -2.454382000 1.785363000 H 2.891720000 -1.592886000 3.339724000 C 4.639554000 -0.411651000 1.588158000 H 5.128620000 0.504171000 1.228282000 H 5.023019000 -0.610011000 2.602684000 H 4.956240000 -1.250590000 0.949867000 C -2.336340000 -1.157112000 -2.492859000 H -1.239253000 -1.088350000 -2.454039000 H -2.619030000 -2.183266000 -2.216721000 H -2.658325000 -0.988570000 -3.533475000 C -4.515377000 -0.303392000 -1.641212000 H -5.059396000 0.491552000 -1.113329000 H -4.817978000 -1.274172000 -1.219844000 C -2.625437000 1.283081000 -2.132182000 H -1.535850000 1.367245000 -2.259401000 H -3.088263000 1.428134000 -3.121919000 H -2.949478000 2.107053000 -1.483111000 C -2.472486000 0.492845000 2.728445000 H -1.554566000 1.083220000 2.602957000 H -3.050018000 0.924147000 3.562146000 H -2.174792000 -0.525274000 3.024236000 C -4.615791000 -0.299263000 1.741129000 H -5.164412000 0.194387000 2.560275000 H -5.288208000 -0.341361000 0.875607000 H -4.407093000 -1.328542000 2.066258000 C -3.703841000 1.936944000 1.095092000 H -4.428579000 1.977092000 0.269533000 H -4.182219000 2.412182000 1.967258000 H -2.841837000 2.558647000 0.812915000 H -4.848912000 -0.285142000 -2.691892000 77 The TS1_Inn for C-CO2 bond formation with (tBuPCP)Pd(CH3) complex (PBE0-D3BJ/BS1, CPCM: Benzene) G298K=-1976.377791 Img. Freq.=-506.124 cm-1 P -2.260815000 0.200545000 0.140335000 P 2.332706000 -0.070421000 0.020257000 C -0.054576000 -2.443228000 0.832585000 H -0.971721000 -2.808797000 1.302796000 H 0.429915000 -1.741656000 1.545825000 H 0.668744000 -3.269492000 0.765134000 C -2.389311000 1.805384000 -0.755940000 H -2.960967000 1.620467000 -1.679339000 H -2.977080000 2.539742000 -0.182493000 C -3.675474000 -0.800184000 -0.618588000 C -2.596046000 0.645089000 1.950132000 C 2.591049000 1.159219000 -1.317954000 H 3.497988000 1.766232000 -1.168389000 H 2.744598000 0.576027000 -2.242049000 C 3.599613000 -1.426073000 -0.348123000 C 2.775792000 0.839259000 1.629371000 Pd -0.005258000 -0.360044000 -0.118554000 C -0.573696000 -2.993749000 -1.078557000 O -0.027921000 -2.386454000 -1.958435000 O -1.306182000 -3.903564000 -0.839303000 C 2.162528000 2.241820000 1.574911000 H 1.094841000 2.223769000 1.324907000 H 2.280310000 2.712695000 2.564611000 H 2.663167000 2.884656000 0.837240000 C 4.277813000 1.002350000 1.860642000 H 4.426809000 1.623943000 2.759045000 H 4.790557000 0.048175000 2.038892000 H 4.772306000 1.517467000 1.023877000 C 2.148406000 0.075599000 2.798994000 H 2.395141000 0.587094000 3.743766000 H 1.053021000 0.047338000 2.707804000 H 2.509838000 -0.959266000 2.875627000 C 4.980117000 -0.877748000 -0.721915000 H 5.484989000 -0.362260000 0.102001000 H 5.618988000 -1.725760000 -1.019775000 H 4.933552000 -0.194352000 -1.582379000 C 3.710512000 -2.379926000 0.842723000 H 4.337448000 -3.240142000 0.556417000 H 4.181231000 -1.910787000 1.717804000 H 2.728868000 -2.770800000 1.145208000 C 3.059789000 -2.200307000 -1.552792000 H 2.070446000 -2.628981000 -1.365374000 H 2.969700000 -1.566305000 -2.447950000 H 3.762968000 -3.013692000 -1.795421000 C -3.230895000 -1.111078000 -2.054044000 H -2.238627000 -1.573709000 -2.106410000 H -3.957197000 -1.802389000 -2.510686000 H -3.205653000 -0.204874000 -2.678490000 C -3.885712000 -2.097956000 0.160635000 H -4.629289000 -2.715483000 -0.369453000 H -2.966403000 -2.692535000 0.237184000 H -4.281668000 -1.907689000 1.168669000 C -5.000349000 -0.033685000 -0.693930000 H -5.702336000 -0.623444000 -1.306317000 H -5.467918000 0.111291000 0.286168000 H -4.899555000 0.948599000 -1.177999000 C -2.245668000 -0.542834000 2.848055000 H -2.413656000 -0.259681000 3.900098000 H -2.858191000 -1.429777000 2.639210000 H -1.191481000 -0.829481000 2.738817000 C -4.031692000 1.090382000 2.220107000 H -4.742125000 0.254927000 2.160531000 H -4.090290000 1.495044000 3.244086000 H -4.365829000 1.883526000 1.534561000 C -1.642381000 1.794906000 2.285868000 H -0.602858000 1.520544000 2.061855000 H -1.875415000 2.717381000 1.734782000 H -1.714908000 2.019626000 3.362325000 C -1.025747000 2.314862000 -1.119795000 C -0.913953000 3.601750000 -1.662014000 C 0.110718000 1.487888000 -0.971914000 C 0.314491000 4.088657000 -2.092687000 H -1.809872000 4.223598000 -1.752851000 C 1.349249000 1.996997000 -1.435412000 C 1.441379000 3.278634000 -1.985513000 H 0.394589000 5.094444000 -2.513098000 H 2.413605000 3.648915000 -2.323308000 42 (MePBP)Pd(CH3) complex (PBE0-D3BJ/BS1, CPCM: Benzene) G298K=-1452.387603 P 1.054677000 -2.226032000 0.000072000 P 1.041492000 2.233056000 0.000058000 N -1.361950000 -1.148479000 -0.000065000 N -1.369203000 1.145214000 -0.000006000 B -0.496855000 0.001175000 -0.000053000 C 3.682270000 -0.011473000 -0.000608000 H 4.073421000 -0.545979000 -0.887327000 H 4.074056000 -0.546406000 0.885571000 H 4.151982000 0.988370000 -0.000536000 C -0.819949000 -2.475993000 -0.000065000 H -1.120507000 -3.057953000 -0.890675000 H -1.120641000 -3.058013000 0.890460000 C 1.616805000 -3.212748000 -1.432090000 C 1.616606000 -3.212770000 1.432297000 C -2.678409000 -0.720603000 -0.000080000 C -3.874828000 -1.430359000 -0.000112000 H -3.873842000 -2.523259000 -0.000147000 C -5.076537000 -0.711567000 -0.000098000 H -6.024981000 -1.254691000 -0.000124000 C -5.080912000 0.685197000 -0.000045000 H -6.032741000 1.222372000 -0.000028000 C -3.883739000 1.411503000 -0.000008000 H -3.889556000 2.504387000 0.000039000 C -2.682902000 0.709242000 -0.000033000 C -0.834293000 2.475626000 0.000186000 H -1.137694000 3.055927000 0.890906000 H -1.137806000 3.056237000 -0.890294000 C 1.599643000 3.222347000 -1.431914000 C 1.599886000 3.222594000 1.431761000 Pd 1.528248000 0.006544000 0.000126000 H 2.715232000 -3.174232000 -1.470721000 H 1.286125000 -4.260550000 -1.364121000 H 1.224909000 -2.762106000 -2.355166000 H 1.224586000 -2.762140000 2.355326000 H 1.285931000 -4.260569000 1.364266000 H 2.715028000 -3.174258000 1.471079000 H 1.263553000 4.268405000 -1.363322000 H 2.698203000 3.189650000 -1.469682000 H 1.210332000 2.770247000 -2.355335000 H 1.263771000 4.268638000 1.363066000 H 1.210759000 2.770637000 2.355330000 H 2.698454000 3.189915000 1.469327000 45 The TS1_Out for C-CO2 bond formation with (MePBP)Pd(CH3) complex (PBE0-D3BJ/BS1, CPCM: Benzene) G298K=-1640.611697 Img. Freq.=-600.2136 cm-1 P 0.030214000 2.471966000 0.000001000 P 0.874416000 -1.953978000 0.000000000 N -2.120612000 0.943357000 -0.000001000 N -1.689022000 -1.310239000 0.000000000 B -1.057555000 -0.021456000 -0.000001000 C 3.140559000 0.687504000 -0.000005000 H 3.474099000 1.725117000 -0.000009000 H 3.128894000 0.162593000 -0.959014000 H 3.128892000 0.162601000 0.959008000 C -1.850312000 2.351102000 -0.000006000 H -2.258740000 2.862070000 0.890818000 H -2.258732000 2.862063000 -0.890838000 C 0.405275000 3.534934000 1.436013000 C 0.405285000 3.534956000 -1.435992000 C -3.332033000 0.270449000 -0.000001000 C -4.641176000 0.740222000 -0.000001000 H -4.849075000 1.813085000 -0.000002000 C -5.682386000 -0.195026000 -0.000001000 H -6.717179000 0.156384000 -0.000001000 C -5.419427000 -1.567166000 0.000000000 H -6.251076000 -2.276154000 0.000000000 C -4.106416000 -2.051615000 0.000000000 H -3.903157000 -3.125350000 0.000001000 C -3.063198000 -1.131591000 0.000000000 C -0.920801000 -2.521278000 -0.000003000 H -1.114306000 -3.145812000 -0.890911000 H -1.114308000 -3.145819000 0.890899000 C 1.635163000 -2.791462000 1.429281000 C 1.635172000 -2.791475000 -1.429269000 Pd 0.910155000 0.356257000 -0.000004000 C 4.905016000 -0.436002000 0.000000000 O 5.827373000 0.313174000 -0.000006000 O 4.525505000 -1.574328000 0.000009000 H 1.491183000 3.704026000 1.474284000 H -0.115566000 4.502392000 1.370801000 H 0.104125000 3.015401000 2.356887000 H 0.104143000 3.015435000 -2.356876000 H -0.115558000 4.502412000 -1.370771000 H 1.491192000 3.704050000 -1.474252000 H 2.712644000 -2.569610000 1.396177000 H 1.209993000 -2.394427000 2.361870000 H 1.480574000 -3.880328000 1.384957000 H 1.480581000 -3.880340000 -1.384937000 H 1.210007000 -2.394447000 -2.361864000 H 2.712652000 -2.569624000 -1.396160000 45 The TS1_Inn for C-CO2 bond formation with (MePBP)Pd(CH3) complex (PBE0-D3BJ/BS1, CPCM: Benzene) G298K=-1640.619433 Img. Freq.=-322.5589 cm-1 P 0.586809000 -2.288562000 0.049016000 P 0.702826000 2.195681000 0.064731000 N -1.761163000 -1.113833000 -0.117117000 N -1.700905000 1.175728000 0.018087000 B -0.867454000 0.005985000 -0.017292000 C 3.074447000 -0.249794000 1.396971000 H 3.467909000 -1.272432000 1.481818000 H 2.389765000 -0.069372000 2.255959000 H 3.899920000 0.461468000 1.540918000 C -1.281558000 -2.462038000 -0.018108000 H -1.578901000 -3.092354000 -0.875309000 H -1.636348000 -2.962046000 0.901781000 C 1.159990000 -2.985146000 -1.533779000 C 1.113450000 -3.513847000 1.293115000 C -3.065273000 -0.643500000 -0.125325000 C -4.280249000 -1.317616000 -0.187420000 H -4.310952000 -2.408212000 -0.249617000 C -5.459450000 -0.564105000 -0.165196000 H -6.423196000 -1.077114000 -0.213270000 C -5.423019000 0.829908000 -0.080110000 H -6.358657000 1.394320000 -0.062031000 C -4.206330000 1.518501000 -0.014574000 H -4.180382000 2.608572000 0.057875000 C -3.028027000 0.780002000 -0.039314000 C -1.138732000 2.472400000 0.270065000 H -1.347691000 2.827602000 1.296154000 H -1.498026000 3.244569000 -0.432791000 C 1.012855000 2.806194000 -1.625758000 C 1.515270000 3.417455000 1.142520000 Pd 1.113110000 -0.059955000 0.321577000 C 3.504352000 0.161532000 -0.722586000 O 3.702192000 1.337328000 -0.803263000 O 3.640550000 -0.910770000 -1.226403000 H 2.248975000 -2.850295000 -1.589858000 H 0.890799000 -4.048031000 -1.627025000 H 0.705370000 -2.411977000 -2.354394000 H 0.748013000 -3.209555000 2.284260000 H 0.740955000 -4.521267000 1.053243000 H 2.212713000 -3.529309000 1.319751000 H 0.762164000 3.874476000 -1.710121000 H 2.072809000 2.641838000 -1.860219000 H 0.397851000 2.224683000 -2.327184000 H 1.187080000 4.444418000 0.921635000 H 1.308030000 3.177122000 2.194876000 H 2.597697000 3.328702000 0.968815000 38 (MePCP)Pd(CH3) complex (PBE0-D3BJ/BS1, CPCM: Benzene) G298K=-1317.625974 P 2.248591000 -0.542146000 -0.030992000 C -0.018740000 1.172945000 -0.000855000 C -0.054630000 3.998526000 0.001231000 C -1.201296000 1.887372000 -0.304896000 C 1.145442000 1.916594000 0.304558000 C -1.217487000 3.286573000 -0.291337000 C 1.125857000 3.315848000 0.292899000 C 3.455711000 -1.567971000 0.873897000 C 0.077852000 -3.007021000 0.002608000 H -0.912178000 -3.492593000 -0.011212000 H 0.634170000 -3.378940000 -0.877573000 H 0.610162000 -3.371109000 0.900446000 C -2.952570000 -0.469659000 1.706562000 C -3.427824000 -1.648965000 -0.870302000 H -2.141393000 3.826788000 -0.521516000 H -0.068471000 5.091905000 0.002034000 H 2.035640000 3.879092000 0.524105000 C -2.434037000 1.096239000 -0.672929000 H -3.373368000 1.573620000 -0.346834000 H -2.500346000 0.973116000 -1.769266000 C 2.398819000 1.158175000 0.673092000 H 3.325116000 1.661121000 0.348215000 H 2.467351000 1.036287000 1.769431000 P -2.237007000 -0.599867000 0.030502000 Pd 0.009592000 -0.906379000 -0.001928000 C 2.965799000 -0.396748000 -1.704695000 H 4.016586000 -0.070693000 -1.663711000 H 2.901410000 -1.367412000 -2.217253000 H 2.374942000 0.336151000 -2.272424000 H 3.446647000 -2.582925000 0.450154000 H 4.473511000 -1.153712000 0.808687000 H 3.152658000 -1.635051000 1.928573000 H -4.451863000 -1.250878000 -0.801472000 H -3.127563000 -1.710933000 -1.926071000 H -3.402590000 -2.663632000 -0.446923000 H -4.010826000 -0.168379000 1.667650000 H -2.864241000 -1.437625000 2.220544000 H -2.377687000 0.277973000 2.271439000 41 The TS1_Out for C-CO2 bond formation with (MePCP)Pd(CH3) complex (PBE0-D3BJ/BS1, CPCM: Benzene) G298K=-1505.839228 Img. Freq.=-634,7467cm-1 P -0.803782000 -1.955008000 0.114484000 C 1.644381000 -0.470198000 -0.049020000 C 4.263881000 -1.494789000 -0.279548000 C 2.721596000 0.367301000 -0.423494000 C 1.912682000 -1.836213000 0.201147000 C 4.019459000 -0.145016000 -0.523329000 C 3.212753000 -2.337967000 0.074268000 C -2.090562000 -2.622488000 1.214134000 C -2.341454000 1.063070000 0.139473000 H -2.393158000 2.138671000 0.302638000 H -2.503497000 0.408347000 0.997997000 C 1.357910000 2.825482000 1.748733000 C 0.239057000 3.754390000 -0.741295000 H 4.844618000 0.515545000 -0.806542000 H 5.278448000 -1.892160000 -0.368014000 H 3.406256000 -3.398246000 0.263503000 C 2.436642000 1.812472000 -0.746827000 H 3.260374000 2.491484000 -0.471487000 H 2.262600000 1.937445000 -1.830788000 C 0.782187000 -2.733409000 0.634553000 H 0.877937000 -3.764343000 0.255983000 H 0.746397000 -2.800216000 1.736945000 P 0.859129000 2.256288000 0.089338000 Pd -0.258169000 0.273898000 0.089421000 C -1.205112000 -2.652943000 -1.519036000 H -1.287444000 -3.749587000 -1.471580000 H -2.165454000 -2.225069000 -1.842724000 H -0.422412000 -2.370639000 -2.237038000 H -3.056362000 -2.213785000 0.880437000 H -2.113295000 -3.722392000 1.173754000 H -1.896590000 -2.297420000 2.246387000 H 0.992371000 4.556933000 -0.729436000 H -0.022483000 3.511240000 -1.781023000 H -0.669805000 4.102399000 -0.229329000 H 2.018792000 3.703469000 1.684176000 H 0.464270000 3.080683000 2.336139000 H 1.884874000 2.003466000 2.253823000 H -2.244800000 0.704010000 -0.891367000 C -4.211661000 0.492506000 -0.265556000 O -4.154053000 -0.688830000 -0.492199000 O -4.929274000 1.442388000 -0.186346000 41 The TS1_Inn for C-CO2 bond formation with (MePCP)Pd(CH3) complex (PBE0-D3BJ/BS1, CPCM: Benzene) G298K=-1505.846570 Img. Freq.=-391.9953 cm-1 P -1.298083000 -1.818511000 0.181373000 C 1.272406000 -0.727004000 -0.053836000 C 3.669210000 -2.141269000 -0.487160000 C 2.414315000 -0.070286000 -0.566298000 C 1.357042000 -2.108477000 0.236094000 C 3.603852000 -0.777913000 -0.768645000 C 2.548369000 -2.805169000 0.007895000 C -2.772346000 -2.286473000 1.133329000 C -2.199630000 1.483117000 1.057200000 H -2.002330000 2.560519000 1.114307000 H -3.280978000 1.307847000 1.126255000 C 1.874108000 2.425904000 1.782540000 C 0.534883000 3.706757000 -0.435409000 H 4.484783000 -0.258770000 -1.158019000 H 4.599471000 -2.690125000 -0.655702000 H 2.601353000 -3.875938000 0.226546000 C 2.308270000 1.397805000 -0.889550000 H 3.265503000 1.935794000 -0.795116000 H 1.945821000 1.544353000 -1.922733000 C 0.135119000 -2.797950000 0.790421000 H 0.073548000 -3.862428000 0.511933000 H 0.120955000 -2.742794000 1.893481000 P 1.005866000 2.077933000 0.216789000 Pd -0.453231000 0.302782000 0.284473000 C -1.592099000 -2.444198000 -1.500874000 H -1.873641000 -3.507990000 -1.477558000 H -2.392299000 -1.843404000 -1.952845000 H -0.670607000 -2.317196000 -2.086461000 H -3.608476000 -1.690710000 0.739429000 H -2.996093000 -3.359203000 1.032879000 H -2.622920000 -2.035505000 2.192999000 H 1.422007000 4.331069000 -0.620266000 H -0.044769000 3.557931000 -1.356096000 H -0.117314000 4.207737000 0.294710000 H 2.662425000 3.181006000 1.639963000 H 1.152523000 2.787625000 2.529425000 H 2.321033000 1.491498000 2.151422000 H -1.787396000 0.991744000 1.966735000 C -2.480319000 1.150805000 -0.928285000 O -3.234394000 0.217417000 -1.059632000 O -2.023079000 2.086802000 -1.530117000 78 (tBuPBP)Ni(CH3) complex (PBE0-D3BJ/BS1, CPCM: Benzene) G298K=-3302.929088 P -2.132898000 -0.579655000 -0.061985000 P 2.137562000 -0.555608000 0.055530000 N -1.134482000 1.808717000 -0.252552000 N 1.095517000 1.823934000 0.198624000 B -0.013125000 0.932460000 -0.025646000 C 0.006800000 -3.004481000 -0.160109000 H -0.375445000 -3.342841000 -1.144016000 H -0.642558000 -3.495752000 0.588560000 H 0.986165000 -3.502100000 -0.063139000 C -2.420472000 1.234080000 -0.496687000 H -2.728496000 1.329984000 -1.552205000 H -3.220631000 1.682656000 0.118207000 C -3.217503000 -1.454264000 -1.339181000 C -4.561433000 -0.775936000 -1.612681000 H -4.448785000 0.259400000 -1.964906000 H -5.220554000 -0.769428000 -0.735705000 H -5.082434000 -1.331564000 -2.410718000 C -3.451807000 -2.908477000 -0.929409000 H -3.909948000 -3.452981000 -1.772042000 H -4.142328000 -2.987554000 -0.077003000 H -2.512099000 -3.413577000 -0.668816000 C -2.370371000 -1.420864000 -2.618776000 H -2.915606000 -1.920692000 -3.436715000 H -1.410275000 -1.934663000 -2.469788000 H -2.153645000 -0.390725000 -2.944099000 C -2.850516000 -0.689529000 1.688528000 C -2.155176000 0.396499000 2.520118000 H -2.497646000 0.314560000 3.565064000 H -2.386210000 1.414100000 2.173705000 H -1.061734000 0.275604000 2.507768000 C -4.361692000 -0.482118000 1.752197000 H -4.677543000 -0.447935000 2.808440000 H -4.912640000 -1.304473000 1.274866000 H -4.677392000 0.463852000 1.286585000 C -2.483264000 -2.047583000 2.291113000 H -1.395001000 -2.198658000 2.284345000 H -2.939463000 -2.887526000 1.750622000 H -2.836327000 -2.087199000 3.335098000 C -0.729596000 3.124959000 -0.167314000 C -1.430335000 4.318869000 -0.307767000 H -2.499753000 4.313675000 -0.533298000 C -0.732064000 5.523102000 -0.154120000 H -1.267796000 6.469852000 -0.260490000 C 0.635588000 5.532429000 0.131301000 H 1.156452000 6.486393000 0.246689000 C 1.352593000 4.337883000 0.273850000 H 2.421838000 4.347421000 0.500029000 C 0.670549000 3.134498000 0.122561000 C 2.381238000 1.268594000 0.483333000 H 2.651791000 1.379183000 1.547031000 H 3.194006000 1.725107000 -0.108419000 C 2.948801000 -0.680229000 -1.648772000 C 2.248372000 0.357731000 -2.535803000 H 2.647826000 0.276612000 -3.560386000 H 2.411586000 1.390574000 -2.195576000 H 1.162444000 0.184138000 -2.577129000 C 4.451312000 -0.408794000 -1.639999000 H 5.010001000 -1.184351000 -1.097565000 H 4.699949000 0.568910000 -1.199857000 H 4.824827000 -0.403416000 -2.677813000 C 2.667211000 -2.066130000 -2.234857000 H 3.048894000 -2.104304000 -3.268817000 H 1.588661000 -2.275592000 -2.251874000 H 3.154221000 -2.871224000 -1.669497000 C 3.167872000 -1.403654000 1.400588000 C 2.210855000 -1.470280000 2.597628000 H 2.723637000 -1.924948000 3.461765000 H 1.323991000 -2.074942000 2.355283000 H 1.862922000 -0.470046000 2.903153000 C 3.560517000 -2.824795000 0.996855000 H 4.316955000 -2.834131000 0.198995000 H 2.694331000 -3.411877000 0.665674000 H 4.000070000 -3.335680000 1.869737000 C 4.432663000 -0.638774000 1.799818000 H 4.960358000 -1.211425000 2.581047000 H 4.214987000 0.351588000 2.222765000 H 5.130414000 -0.507961000 0.962357000 Ni 0.006269000 -0.997657000 -0.044280000 81 The TS1_Out for C-CO2 bond formation with (tBuPBP)Ni(CH3) complex (PBE0-D3BJ/BS1, CPCM: Benzene) G298K=-3491.147873 Img. Freq.=-592.8321 cm-1 P 0.950265000 1.917306000 -0.162441000 P -0.628689000 -2.092004000 -0.035637000 N -1.639471000 1.827913000 -0.200270000 N -2.426038000 -0.249079000 0.298768000 B -1.221503000 0.464324000 -0.023773000 C 2.473137000 -1.050727000 -0.399343000 H 2.937318000 -0.373372000 -1.110382000 H 2.340325000 -2.084068000 -0.698660000 H 2.405345000 -0.770620000 0.660527000 C -0.660212000 2.823764000 -0.505252000 H -0.755928000 3.731741000 0.115310000 H -0.700948000 3.142192000 -1.560809000 C 1.395634000 2.488888000 1.585243000 C 2.109274000 2.638516000 -1.469987000 C -3.001249000 1.929150000 0.008618000 C -3.863755000 3.019804000 -0.040507000 H -3.489691000 4.016497000 -0.287496000 C -5.219832000 2.806271000 0.232747000 H -5.911795000 3.651549000 0.199719000 C -5.701669000 1.532215000 0.545303000 H -6.765401000 1.394111000 0.754586000 C -4.844077000 0.427201000 0.596710000 H -5.222320000 -0.567601000 0.844967000 C -3.493845000 0.627028000 0.326977000 C -2.359645000 -1.652863000 0.559103000 H -3.133793000 -2.232046000 0.026417000 H -2.462505000 -1.880083000 1.633636000 C -0.090089000 -3.392883000 1.230468000 C -0.950978000 -2.827077000 -1.748618000 C 4.308626000 -1.448764000 0.448627000 O 4.944687000 -0.436897000 0.392866000 O 4.283238000 -2.588950000 0.805353000 C -1.765316000 -1.784130000 -2.525713000 H -1.239849000 -0.818828000 -2.581245000 H -1.915131000 -2.149720000 -3.554848000 H -2.758460000 -1.604409000 -2.089691000 C -1.719896000 -4.145841000 -1.711272000 H -1.962383000 -4.450165000 -2.742982000 H -1.129956000 -4.957317000 -1.263003000 H -2.671028000 -4.063529000 -1.163827000 C 0.382112000 -3.019355000 -2.476566000 H 0.183647000 -3.407754000 -3.489046000 H 0.922673000 -2.067403000 -2.574565000 H 1.044758000 -3.734461000 -1.970723000 C -1.227314000 -4.329873000 1.649679000 H -1.608155000 -4.933363000 0.816370000 H -0.842039000 -5.028108000 2.410982000 H -2.074236000 -3.797318000 2.104099000 C 1.087559000 -4.232980000 0.733698000 H 1.389818000 -4.919711000 1.541500000 H 0.820204000 -4.853959000 -0.133188000 H 1.972095000 -3.629270000 0.489397000 C 0.363350000 -2.574227000 2.446802000 H 1.264737000 -1.987865000 2.218580000 H -0.416322000 -1.881308000 2.802187000 H 0.608082000 -3.256049000 3.277589000 C 0.163680000 2.260188000 2.470431000 H -0.171921000 1.212737000 2.442076000 H 0.430755000 2.503651000 3.511891000 H -0.688017000 2.896560000 2.189932000 C 2.532271000 1.610105000 2.117447000 H 2.850026000 1.989431000 3.102377000 H 2.192373000 0.574123000 2.263147000 H 3.414943000 1.580720000 1.465573000 C 1.791722000 3.962448000 1.656290000 H 1.932055000 4.245011000 2.712734000 H 2.737819000 4.166127000 1.136714000 H 1.016503000 4.625013000 1.242305000 C 3.576642000 2.407940000 -1.103402000 H 4.203334000 2.657232000 -1.975576000 H 3.897278000 3.061569000 -0.279505000 H 3.809086000 1.373827000 -0.813733000 C 1.888140000 4.131683000 -1.729642000 H 2.086650000 4.750656000 -0.846027000 H 2.584188000 4.456667000 -2.520763000 H 0.872546000 4.354362000 -2.086109000 C 1.763059000 1.858945000 -2.746183000 H 1.966742000 0.784765000 -2.634216000 H 0.701721000 1.968762000 -3.021796000 H 2.366505000 2.241023000 -3.585867000 Ni 0.545122000 -0.245314000 -0.181204000 81 The TS1_Inn for C-CO2 bond formation with (PBE0-D3BJ)Ni(CH3) complex (ωB97XD/BS1, CPCM: Benzene) G298K=-3491.139961 Img. Freq.=-353.0754 cm-1 P -2.118116000 -0.704522000 0.033506000 P 2.191437000 0.021734000 -0.172885000 N -1.393063000 1.684996000 0.664930000 N 0.697603000 2.128825000 -0.102164000 B -0.172608000 1.041248000 0.253748000 C 0.250488000 -2.732303000 -1.061084000 H -0.405584000 -3.607900000 -0.938529000 H -0.254143000 -2.114049000 -1.830937000 H 1.195712000 -3.083034000 -1.490126000 C -2.546386000 0.882220000 0.935002000 H -3.475421000 1.336855000 0.561536000 H -2.680454000 0.688146000 2.010600000 C -2.772271000 -0.350642000 -1.732503000 C -3.215601000 -1.971737000 0.921280000 C -1.265688000 3.055616000 0.551901000 C -2.160299000 4.090382000 0.807253000 H -3.166294000 3.880594000 1.179212000 C -1.736261000 5.405032000 0.579803000 H -2.425537000 6.230411000 0.774990000 C -0.448205000 5.678017000 0.111622000 H -0.143036000 6.714019000 -0.055596000 C 0.459658000 4.645000000 -0.150089000 H 1.464438000 4.859348000 -0.522652000 C 0.047606000 3.334546000 0.069784000 C 2.008249000 1.841823000 -0.588321000 H 2.793242000 2.449388000 -0.105792000 H 2.095834000 1.995248000 -1.678061000 C 3.343297000 -0.562447000 -1.556468000 C 3.090915000 0.117661000 1.501989000 C 0.901915000 -3.181623000 0.986465000 O 0.156213000 -2.755909000 1.813889000 O 1.823980000 -3.869029000 0.707513000 C 2.263097000 1.032295000 2.413949000 H 1.225356000 0.680013000 2.509122000 H 2.718289000 1.023400000 3.417886000 H 2.238992000 2.075843000 2.069665000 C 4.508471000 0.677881000 1.394757000 H 4.900102000 0.838607000 2.412770000 H 5.192013000 -0.020205000 0.892584000 H 4.550467000 1.645959000 0.874028000 C 3.143208000 -1.264058000 2.155414000 H 3.731008000 -1.192473000 3.085371000 H 2.137505000 -1.607357000 2.427842000 H 3.609503000 -2.028046000 1.521360000 C 4.472338000 0.416606000 -1.891453000 H 5.190055000 0.544085000 -1.073730000 H 5.029512000 0.019221000 -2.756259000 H 4.098768000 1.409358000 -2.181635000 C 3.930151000 -1.929338000 -1.203900000 H 4.410755000 -2.360625000 -2.097628000 H 4.702949000 -1.849014000 -0.425335000 H 3.165843000 -2.635566000 -0.850905000 C 2.445656000 -0.686242000 -2.794933000 H 1.659456000 -1.437053000 -2.658329000 H 1.965719000 0.270213000 -3.056319000 H 3.063274000 -0.988904000 -3.656557000 C -1.672828000 0.405375000 -2.491394000 H -0.745470000 -0.178575000 -2.574010000 H -2.031172000 0.620285000 -3.512239000 H -1.422766000 1.362712000 -2.012839000 C -3.043034000 -1.669091000 -2.462545000 H -3.251392000 -1.449070000 -3.522524000 H -2.180578000 -2.349871000 -2.430674000 H -3.918532000 -2.197620000 -2.061345000 C -4.033988000 0.514828000 -1.766154000 H -4.381958000 0.585267000 -2.809982000 H -4.860544000 0.104945000 -1.172187000 H -3.835994000 1.542462000 -1.428825000 C -2.884201000 -3.390281000 0.454230000 H -3.527982000 -4.100645000 0.998788000 H -3.055959000 -3.542885000 -0.618317000 H -1.840689000 -3.636946000 0.681181000 C -4.707938000 -1.692439000 0.743887000 H -5.050156000 -1.858371000 -0.286900000 H -5.276453000 -2.382046000 1.390278000 H -4.981897000 -0.668626000 1.041282000 C -2.869164000 -1.880528000 2.415308000 H -1.784780000 -1.915958000 2.583984000 H -3.283551000 -0.979623000 2.889167000 H -3.315139000 -2.747742000 2.929122000 Ni 0.138981000 -0.833042000 -0.064071000